Zvonareva, a last-minute replacement for Svetlana Kuznetsova, dropped the opening set in the first reverse singles match, but rallied for a 4-6 6-3 6-2 victory.
"I haven't played for my country for a couple of years," Zvonareva said. "It's a pleasure for me to be back in the team. All the girls are really good, the coaches are great and I'm just happy to be part of the best team in the world."
The win assured a successful title defense and put Russia in the Fed Cup final for the fourth time in the last five years.
In a meaningless match, Anna Chakvetadze downed Ahsha Rolle 6-4 7-5.
Russia will face Spain in September in the Fed Cup final.
Spain surprised favored China 4-1 in Beijing.