Great Britain, who have secured medals in the last three Olympic Games and earned bronze in Tokyo 2020, suffered a 3-0 defeat against Tokyo silver medalists Argentina.
Despite the loss, GB had already secured a spot in the quarter-finals.
The 2016 champions finished the pool stage in fourth place, with two victories and three losses in their five matches.
In the upcoming quarter-finals, Great Britain will face the Netherlands, who defeated them 5-1 in the Tokyo semi-finals before claiming the gold medal by beating Argentina.
During Saturday's match, GB's Tess Howard received a yellow card early in the third quarter, and during her absence, Valentina Raposo and Agustina.
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