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The Old Maids Club is a group started by Sue in Hell-O, the fourteenth episode of Season One.
After Rachel was dumped by Finn and met Jesse in the music store, Sue rounded up a group of unpopular girls (or, as Sue puts it, "Mustache-sporting teenage girls with glandular conditions". Most of the girls had failed love attempts, and some, such as Lauren Zizes, had stories very similar to Rachel's.) to try to convince Rachel to date Jesse against the Glee Club's wishes, which would help Sue in her attempt to break up the New Directions. It is unknown whether the club still exists, but it's unlikely, as the only reason it was formed was for Sue to try to break up the Glee Club.