The experienced coach replaces Brian Ross, who stepped down earlier in the season.
Kenny Aitchison also comes in as assistant coach.
The club posted on Twitter: “Willie brings a wealth of top level coaching and scouting experience to the team which has already been a welcome addition to the season so far.”
Aitchison is a former first-team, reserve and academy coach at Hearts, working under Csaba Laszlo at Tynecastle in the Vladimir Romanov era.
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He has also managed East Fife, and coached at Cowdenbeath.
City’s women, who play their home matches at Broxburn’s Albyn Park and have ambitions to climb the women’s pyramid, are currently one point clear at the top of the third tier Scottish Women's Championship South, with nine wins from their 11 games so far.
Aitchison’s first game in charge could come this Sunday when City host Gartcairn.