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Monica and Chandler get together during Season 4 Episode 24 The One with Ross's Wedding. Monica is sad that people think she is Ross's mother and she is depressed at the wedding. Eventually she sleeps with Chandler and that is how their relationship started. Later in the series, we learn that when she was drunk and knocked on Chandler and Joey's hotel room, she was really looking for Joey to sleep with. This caused a small rift in the relationship but eventually they make up and get married.

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Q: What episode do monica and chandler sleep together before a wedding?
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