Englishman Matthew, the reigning and three-time World Champion from Sheffield who struck gold in the Men's Singles and Men's Doubles in the 2010 Games in Delhi, will begin his title defence against Xavier Koenig, a 29-year-old Mauritian making his Games debut.
Nicol David, the women's world No1 since August 2006 who is celebrating a record-equalling fifth successive appearance in the Games since 1998, lines up against Vanessa Florens, a 34-year-old from Mauritius who also competed in the 2006 Games in Melbourne.
Mauritius, with a population of just over 1 million, boasts only a handful of squash courts and neither Koenig nor Florens - the only two Mauritians competing in the squash events in Glasgow - have ever been world-ranked.
Top seed Matthew, ranked two in the world and aged 33, is expected to meet Guernsey's world No23 Chris Simpson, the No7 seed, in the quarter-finals before a predicted clash with England team-mate Peter Barker, the third seed and bronze medallist in 2010, in the semi-finals.
Second seed James Willstrop is Matthew's anticipated opponent in a repeat of the 2010 all-English final. Willstrop, also a Yorkshireman, from Harrogate, begins his third Commonwealth Games campaign against Bermuda's Nicholas Kyme, a 33-year-old Games veteran since 2002. 30-year-old Willstrop, a former world No1 currently ranked six in the world, is drawn to meet Botswana Games debutant Alister Walker in the quarter-finals before a semi-final battle with former Pontefract club-mate Saurav Ghosal, the No4 seed from India.
In the women's event, 30-year-old Penangite David is expected to renew her career-long rivalry with England's No8 seed Jenny Duncalf in the quarter-finals in what would be a repeat of the Delhi final. Third-seeded New Zealander Joelle King, a double medallist in Delhi, is predicted to be David's semi-final opponent.
The climax is expected to be a repeat of the last two British Open finals between David and Laura Massaro, the World Champion from England who is the event's No2 seed. Massaro first meets Lynette Vai, a Games debutante from Papua New Guinea playing the biggest match of her life three days after her 16th birthday.
Awaiting Massaro in the quarter-finals should be Malaysian Low Wee Wern, the fifth seed, with fourth-seeded England team-mate Alison Waters her likely opponent in the semis.
Pools have also been set in the Men's, Women's and Mixed Doubles events - for details, see below.
Glasgow 2014 squash action takes place at the Scotstoun Sports Campus - with Singles from 24-28 July, followed by Doubles from 29 July to 3 August.
Women's Singles: Round 32 draw
 Nicol David (MAS) v Vanessa Florens (MRI)
 Megan Craig (NZL) v Safina Madhani (KEN)
 Jenny Duncalf (ENG) v Amanda Landers-Murphy (NZL)
 Samantha Cornett (CAN) v Sarah Cardwell (AUS)
 Joelle King (NZL) v Winner of Sarah Taylor (JEY) v Violet Luchendo (KEN)
 Joshana Chinappa (IND) v Winner of Deon Saffery (WAL) v Kimberley Borg-Cauchi (MLT)
 Madeline Perry (NIR) v Winner of Dorothy Boyce (PNG) v Sharon Chimfwembe (ZAM)
 Kasey Brown (AUS) v Winner of Eva Alphonse (SEY) v Nadindhi Udangawa (SRI)
 Delia Arnold (MAS) v Winner of Khaaliqa Nimji (KEN) v Anaka Alankamony (IND)
 Dipika Pallikal (IND) v Winner of Charlotte Knaggs (TTO) v Naduni Gunawardane (SRI)
 Rachael Grinham (AUS) v Winner of Mihiliya Methsarani (SRI) v Colette Sultana (MLT)
 Alison Waters (ENG) v Eli Webb (PNG)
 Tesni Evans (WAL) v Kerrie Sample (TTO)
 Low Wee Wern (MAS) v Eilidh Bridgeman (CAY)
 Nicolette Fernandes (GUY) v Namweene Muchaile (ZAM)
 Laura Massaro (ENG) v Lynette Vai (PNG)
POOL 1:  Jenny Duncalf & Laura Massaro (ENG),  Tesni Evans & Deon Saffery (WAL), Lynette Vai & Eli Webb (PNG), Charlotte Knaggs & Kerrie Sample (TTO)
POOL 2:  Kasey Brown & Rachael Grinham (AUS),  Lisa Camilleri & Donna Urquhart (AUS), Delia Arnold & Vanessa Raj (MAS), Kimberley Borg-Cauchi & Colette Sultana (MLT)
POOL 3:  Emma Beddoes & Alison Waters (ENG),  Joelle King & Amanda Landers-Murphy (NZL), Alex Clark & Frania Gillen-Buchert (SCO), Dorothy Boyce & Sheila Morove (PNG)
POOL 4:  Nicol David & Low Wee Wern (MAS),  Joshana Chinappa & Dipika Pallikal (IND), Megan Craig & Kylie Lindsay (NZL), Mihiliya Methsarani & Nadindhi Udangawa (SRI)
POOL 1:  Kasey Brown & Cameron Pilley (AUS);  Rachel Arnold & Valentino Bon Jovi Bong (MAS), Nicolette Fernandes & Alexander Arjoon (GUY)
POOL 2:  Joelle King & Martin Knight (NZL);  Alex Clark & Kevin Moran (SCO), Sarah Taylor & Nick Taylor (JEY)
POOL 3:  Rachael Grinham & David Palmer (AUS),  Madeline Perry & Michael Craig (NIR), Marlene West & Cameron Stafford (CAY), Sharon Chimfwembe & Manda Chilambwe (ZAM)
POOL 4:  Alison Waters & Peter Barker (ENG),  Tesni Evans & Peter Creed (WAL), Charlotte Knaggs & Colin Ramasra (TTO), Colette Sultana & Daniel Zammit-Lewis (MLT)
POOL 5:  Dipika Pallikal & Saurav Ghosal (IND),  Samantha Cornett & Shawn Delierre (CAN), Naduni Gunawardane & Ravindu Laksiri (SRI)
POOL 6:  Sarah Kippax & Daryl Selby (ENG),  Deon Saffery & David Evans (WAL), Kerrie Sample & Kale Wilson (TTO), Vanessa Florens & Xavier Koenig (MRI)
POOL 7:  Amanda Landers-Murphy & Paul Coll (NZL),  Joshana Chinappa & Harinder Pal Sandhu (IND), Eli Webb & Schubert Maketu (PNG)
POOL 8:  Delia Arnold & Mohd Nafiizwan Adnan (MAS),  Frania Gillen-Buchert & Alan Clyne (SCO), Eilidh Bridgeman & Daniel Murphy (CAY), Lynette Vai & Madako Junior Suari (PNG)