Venus Williams saw her hopes of winning a sixth Wimbledon title ended by Dutchwoman Kiki Bertens in a Court One marathon.
The American ninth seed had battled back from a set and a break down to haul herself level.
And Bertens, seeded 20th, had to call on all her reserves of energy to see off 38-year-old Williams 8-6 in the deciding set in a match lasting two hours and 40 minutes.
After Madison Keys lost earlier on Friday, Williams became the eighth of the top 10 seeds to go out in the early rounds at this year's championships.
Keys, who was the US Open runner-up last year, crashed out 7-5 5-7 6-4 to the Russian on a baking hot Court Three.
The 23-year-old American threatened a remarkable comeback in the third-round contest, coming from a set and 4-0 down to force a decider.
But Rodina, 29, held her nerve to reach the last 16 at a grand slam for the first time.
Williams said after the 6-2 6-7 (5/7) 8-6 defeat: "I just ran out of time in the end. She played really well, you have to win the last point and I didn't succeed in that today.
"The third set was really competitive, it was just toe-to-toe.
"Of course, you know that the plan is to go out and try and win the matches. I think she was a little bit luckier than I was in the end. Sometimes it takes luck and skill and she definitely deserved to win."
When asked if she would be back at the championships next year, Williams said: "Yeah."
