Spencer takes over the captaincy armband from Wasps player Sue Day who announced her international retirement last month.
Spencer, who lives in Brislington in Bristol but is originally from Ashford in Kent, has 27 caps for England and plays at No.8.
The 28-year-old, who first started playing rugby at Folkestone RFC, was part of the 2007 RBS 6 Nations Grand Slam winning team and last year featured in the final of the IRB Women’s Rugby World Cup.
Spencer’s first game in charge will come on December 15th when England take on the USA at London Irish ARFC, kick-off 230pm. England then begin their defence of the RBS 6 Nations on February 2nd against Wales also at London Irish AFRC.
England Head Coach Gary Street said: “With three Six Nations championships and a Rugby World Cup final under her belt Catherine will bring a wealth of experience to the team as captain. She has demonstrated the maturity needed as a skipper both on and off the pitch - she has certainly got a wise head on young shoulders.
“Catherine’s game is improving all the time and she is one of the best No. 8’s in European rugby. Her self assurance and her strong physical presence on the pitch also makes her a natural choice for captain. Her good rugby understanding will also help to implement what we want as coaches both on and off the pitch.”
Spencer added: “I am absolutely delighted to have been given this opportunity. It is a massive honour and I am very excited and very proud to be named captain. I am following in the footsteps of some great past captains, including the likes of Sue Day and Jo Yapp most recently; they are all players that have been heroes in my eyes.
“This year we have quite a new looking elite squad but I think it will be another strong year for us. Over the past couple of years, we have had strength in depth and that is really coming to the fore now. We have some very exciting new players coming through the ranks as well as a strong mix of experienced heads.
“Our first international of the season is against the USA, a side our England A team play just a couple of days earlier. It is great that we now have autumn international fixtures and having played them recently in the 2006 Women’s Rugby World Cup we know that they will be very tough opposition but we are all looking forward to the challenge.”
Saracens centre Rachel Burford has been named Vice Captain. Burford, who lives in Walthamstow but is originally from Medway in Kent, has seven caps for England since making her debut against South Africa in the 2006 IRB Rugby World Cup.
Street added: “Rachel is another youngster that has demonstrated she has got a lot to give England rugby and I think she is an ideal choice to assist Catherine. Like Catherine she has come through the successful RFUW academy system and has a great game understanding. She captained our sevens programme last year and showed both natural ability and confidence. I am looking forward to working with both players this season.”