World number 2 and defending Wimbledon champion Roger Federer is still the player to beat at the most prestigious tennis event, reaching the fourth round for the 16th time (16-0 in the third round matches) after a commanding 6-3 7-5 6-3 win over Jan-Lennard Struff in just an hour and 34 minutes.
Five-time Wimbledon champion Venus Williams could not pull off a third consecutive comeback, instead joining the parade of top-10 seeds on the way out of the Grand Slam tournament.
Rodina won nine games in a row to move a set and two breaks ahead before Keys recovered from 4-0 down in the second set to set up a decider.
Serena will play world number 120 Rodina if she advances to the fourth round.
Later Thursday, fifth-seeded Juan Martin del Potro, who made the semi-finals in 2013, tackles 36-year-old Feliciano Lopez, a three-time quarter-finalist, who is playing in a record 66th consecutive major.
Her sister Serena Williams is still going strong, though, after overcoming her toughest test so far this week.
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Monfils is another fourth round debutant after he knocked out last year's semi-finalist Sam Querrey 5-7 6-4 6-4 6-2.
Keys lost in three sets behind a faltering serve, and gave up seven break points to Rodina. After the double fault in the first set, Mladenovic appeared to lose her confidence.
"Honestly, I think today was a massive mishandle of nerves", Keys said.
Unseeded American Taylor Fritz also unexpectedly took a 2-1 lead over world No. 4 and tournament fourth seed Alexander Zverev before their second round match suspended by darkness.
Nick Kyrgios, the 15th seed, also advanced in straight sets, beating Dutchman Robin Haase 6-3 6-4 7-5 to book a date with Kei Nishikori, who ousted Kyrgios's fellow Australian Bernard Tomic 2-6 6-3 7-6 (9-7) 7-5.
The 29-year-old Russian needed treatment after securing the decisive break in the final set, but she was able to block out the pain to seal her upset.