The 32-year-old American, who suffers from Sjogren's Syndrome, was beaten 6-1 6-3 by the Russian world number 79.
"There's no way I'm going to sit down and give up," said Williams.
"I don't have time to feel sorry for myself, it doesn't feel good. I'm going to use the time to feel positive. I love this sport."
Williams held serve only once as she was blown away in the first set.
She recovered in the second, but when Vesnina broke in the sixth game she closed out victory to hand Williams only her second first-round defeat at the All England Club.
The other time that the seven-time Grand Slam champion fell at the first hurdle was in her debut year at SW19, in 1997, also the only other occasion when she was unseeded.
Only two women have won more Wimbledon titles in the open era, but Williams has not lifted the Rosewater Dish since 2008.
READ MORE:.http://www.bbc.co.uk/sport/0/tennis/18582668
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