Russian-born Rodionova saw off the world-ranked 64 Duan in straight sets, 7-5, 6-4, in one hour and 42 minutes in sweltering Nanchang, southeastern China.
Fifth seed Duan, standing at over six feet (1.82 metres), towered over the diminutive Rodionova.
But that counted for nothing as the 27-year-old Australian powered a forehand winner to seal a convincing victory on the Jiangxi Open hard courts.
"It was really tough conditions, it's very humid," Rodionova told the WTA website.
"I was preparing myself for it. I think today it was a little bit hard for both of us. I'm glad to manage to get through."
Serbia's Jelena Jankovic, 32, a former world number one, made it a second Chinese loser on the day as she swatted aside Kang Jiaqi 6-2, 7-5.
But three other home players -- Wang Yafan, Lu Jingjing and Zhu Lin -- were all victorious to get into the second round.
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