The No.1-seeded Li had lost four of her last five meetings against Zvonareva but after such a great 2013 season - and given Zvonareva had been out of action 17 months due to illness and a shoulder injury - the Chinese had an edge this time, and after an hour and 46 minutes she prevailed, 75 63.
"I'm happy with my performance today," Li said. "This was the first match of the new season for both of us and the first match is not always easy. It's been about two months since my last match, and during the off-season I was practicing indoors in Beijing, so I'm still trying to get used to playing outdoors."
Despite the loss, Zvonareva - who is currently unranked but was given a wildcard into the International-level event - remained positive about just being back in the swing of things again on the tour.
"It felt great," she said. "I enjoyed the atmosphere on the court today. That's what I've been missing for a very long time. It was an excellent opportunity to get that feeling back. I was actually very happy that I got the chance to play Li Na in the first round - it gave me an opportunity to play on center court in front of a big crowd, and I really enjoyed the moment. I got some really great experience out there today.
"I also know what I have to work on and improve, and hopefully I'll do a little bit better next time."
There was certainly no void for Zvonareva during her 17 months off - she kept very busy with shoulder rehab after undergoing surgery, as well as obtaining her degree in international economic relations from the Diplomatic Academy of the Ministry of Foreign Affairs of the Russian Federation (read more).
So is her outlook on life - and on tennis - any different now after accomplishing so much off the court?
"I guess it's a little different now," she said. "Everyone grows up and gets more experienced, and I think I'm more mature and experienced than I was before. I've done some other things now. I've seen the world a little bit more outside of tennis. It was different and great, but I'm happy to be back here."
Zvonareva's accomplishments on the court are vast - two-time Grand Slam finalist, former World No.2 - but she's in no hurry to set any goals on this comeback. "The most important thing for me is to enjoy my game and enjoy being out there, playing with no pain, playing big matches and fighting for every point. That's my goal. Whatever happens happens - there's no reason to set something right away.
"I've been on the tour for so many years and now I just want to enjoy playing."