AN unpredictable Olympic tennis tournament claimed its biggest scalp of all as Serena Williams crashed out in the third round of the women's singles.

The world number one appeared to have a shoulder problem and was close to tears as she lost 6-4 6-3 to Ukraine's Elina Svitolina.

Serena and sister Venus are the most successful players in Olympic tennis history with four gold medals each but Rio has been dreadful for the family.

Venus lost in the opening round of the singles to Kirsten Flipkens while the sisters lost their first ever Olympic doubles match on Sunday.

Serena won gold in both events in London four years ago and appeared to have put doubts about her form to bed by winning her 22nd grand slam singles title at Wimbledon last month.

The 34-year-old's exit means Angelique Kerber and Madison Keys are the only top-eight seeds remaining of what had appeared a very strong field.

Serena looked like she might turn things around when she recovered from 1-3 to 3-3 in the second set but then dropped serve again after serving five double faults in one game.

In the final game, she was rolling her usually-fearsome serve over the net and, although she saved two match points, she drove a forehand wide on the third.

Serena pulled out of a tournament in Montreal two weeks prior to the Olympics with a shoulder problem and it appears that has resurfaced.

The top seed declined to speak to the press but gave a brief interview to a member of the US support team.

Sounding hoarse, she said: "The better player today won but I can't wait for next time and I know next time is going to be a really good match and I look forward to it.

"It was a great opportunity. It didn't work out the way I wanted it to but at least I was able to make it to Rio, that was one of my goals."

Asked if she got the impression Serena was injured, Svitolina, the world number 20 and 15th seed here, said: "Yes I got the feeling but I was trying to stop thinking about it, just stay in the moment and play the ball, don't play against Serena Williams and Olympic champion, so many grand slams.

"Even at that moment I didn't expect that I could win. I think that helped me a lot, don't expect a mistake from her and just fight and be focused."

The 21-year-old now has her sights set on the biggest prize, saying: "For me the Olympics is just unreal. To win a gold medal in the Olympics is so special and if I can do it it's going to be just unreal."

The tournament has now lost the top seeds in men's and women's singles and doubles, while Andy Murray is the only defending champion remaining.