Amaya Valdemoro poured in 26 points and grabbed eight rebounds as the Spanish clawed their way back from a 44-24 deficit at half-time to trail 69-65 in the final minute.
Evaristo Perez’s team could have trimmed the deficit to just two with 21 seconds left but a Valdemoro lay-up rimmed out and Russia ultimately triumphed by six to capture the title and qualify for next year’s Olympics in Beijing.
"This is a big relief and I am very happy," said Russia center Maria Stepanova, who was voted to the all-tournament team after scoring eight points, hauling down 10 boards and blocking three shots.
"I almost forgot that by winning the gold medal we qualified for the Olympics."
Ilona Korstin led Russia with 18 points and seven rebounds while Tatiana Shchegoleva scored 14.
Russia’s victory has capped a great summer for Russian basketball because the men’s team also won the gold medal, beating Spain at that EuroBasket in Madrid three weeks ago.
This marked the first time that the same two countries met in the gold medal games of both the men’s and women’s EuroBaskets.
Spain’s women will now join bronze medal winners Belarus, fourth-placed Latvia and the fifth-placed Czech Republic in the pre-Olympic qualifying tournament.
"I knew my team was going to react because throughout the tournament and in the past, we’ve shown a lot of heart and pride," Perez said.
"It’s a pity we reacted too late. Russia are a very difficult team to play against. There is a physical difference and they are a great team."
Russia out-rebounded Spain 40-33.
"But I would like to point out that Spain not only have heart and pride, but we also know how to play basketball."
Russia won the gold medal four years ago at the EuroBasket in Greece and finished runners-up to the Czechs in Turkey in 2005.
After snatching silver at the 2006 FIBA World Championship in Brazil, they entered this tournament as title favourites.
They lost a qualifying round game to Serbia but underlined their championship credentials with a decisive win over Spain.
Perez, who coached in his first EuroBasket, guided his team past Belgium and Belarus in the quarter-finals and semi-finals, respectively, while Russia put paid to the hopes of Lithuania and Latvia.
By half-time, the Russians had one hand on the title after a strong defensive and rebounding performance in which they came up with nine steals and out-rebounded Spain 23-16.
But Spain never quit and with Valdemoro’s heroics and Laia Palau (18pts), they battled back but came up just short.
Valdemoro, who is a CSKA Moscow teammate of Stepanova, Korstin, Olga Arteshina and, said: "I told my teammates in the Russian team they always play in these types of games but for us it’s so difficult just to get here.
"We’re not the biggest team, like I’ve said so many times before, but what we do have is a lot of heart."
Belarus survived a furious comeback by Latvia to win 72-63 and capture the bronze medal in their very first appearance at the EuroBasket Women.
Anatoli Buyalski’s team led by as many as 25 points late in the third quarter but had to hold on for dear life as the Baltic side closed the gap to 61-57 with 3:29 to go on Ieva Kublina’s four-point play.
That capped a 20-4 run and almost everyone, including Latvia President Valdis Zhtlers who was sitting courtside after arriving in Chieti for Sunday’s game, was standing on their feet and cheering.
After Belarus’ Nataliya Trafimava and Latvia’s Jansone exchanged baskets, the team from Minsk did just enough to preserve victory.
The outstanding point guard Natalie Marchanka found Tatyana Troina open in the corner and the deadly three-point shooter struck for a 66-59 lead with 2:31 to go and Belarus pulled away for a nine-point triumph.
Marchanka, who finished with nine points, seven assists and three rebounds, said: "We are writing the history of Belorussian basketball.
"I'm very proud of my team and I am just happy to be a part of it.
"I will continue to work hard and achieve something higher than this."
The pill was tough to swallow for Latvia, who won over most of the neutrals at the EuroBasket with the dynamic play of point guard Gunta Basko and shooting guard Anete Jekabsone-Zogota.
In the battle for fifth place, the Czechs thrashed Lithuania 93-54 to earn the last place on offer for Europe to compete in the pre-Olympic qualifying tournament.
Jeff Taylor and Cindy Garcia-Bennett, Chieti