Bedford, who has been working for the Football Association since 2014, will start her role on 6 December and replaces Jonathan Morgan in the position he held for seven years.
Morgan was sacked just a week ago as Leicester have failed to win a point this season – their first in the top flight.
“Leicester City’s vision for women’s football and the extent of its ambition have been obvious during the last two seasons,” Bedford said.
“I’m unbelievably excited to have the chance to be part of that. Taking the step into a senior coaching role is something I’ve always wanted to do.”
This will be the coach’s first time managing in the WSL but she has been involved in the Championship with Tottenham and London Bees.
Bedford’s first match in charge will be against league leaders and unbeaten Arsenal with Emile Heskey, Leicester’s head of women’s football development, overseeing training in the meantime.
It has been the most brutal opening to a WSL season for managers, with three being sacked in the opening eight rounds. Morgan, Everton’s Willie Kirk and Birmingham City’s Scott Booth have all been given the boot in this campaign.
Kirk has since been replaced by Jean-Luc Vasseur and Darren Carter has been named as an interim coach for Birmingham until they find a long-term replacement for Booth.
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