Gauff endures doubles disappointment at Paris Olympics
In her first game of the day, Gauff teamed up with world number six Jessica Pegula to face Czech Republic duo Karolina Muchova and Linda Noskova.
After taking the first set, Gauff and Pegula were unable to continue their momentum, falling to a 6-2 4-6 5-10 defeat.
The American pairing started strongly and raced into an early lead, taking the opening set in what seemingly looked like a straightforward victory for Team USA.
However, Muchova and Noskova rallied and in a second set that saw five break points converted by both, the Czech's would prevail to take the game to a decider.
Gauff and Pegula lost four straight games to put their opponents in the ascendency, with Muchova and Noskova able to see out the win to progress to the quarter-finals.
Gauff emerged back onto the clay courts in the French capital for her mixed-doubles match soon after, joining Taylor Fritz to face a Canadian pairing of Felix Auger-Aliassime and Gabriela Dabrowski.
The American duo would come from a set down to take the game to a decider, but it would be their opponents who emerge 6-7 (2-7) 6-3 8-10 victors.
Gauff and Fritz exchanged blows with the Canadians, but were edged out in a first set tie-break after losing four games on the spin.
But not wanting to let their dreams of a medal die, the American pair would recover from losing an early break point to rally and earn one of their own in the eighth game, seeing out the win to take Gauff to her second third-set decider of the day.
However, the same result would transpire, with Auger-Aliassime and Dabrowski edging a nail-biting conclusion to book their place in the quarter-finals of the competition.