Monyepao -- who has earned a masters degree in sport management from Loughborough University in the United Kingdom and worked on the 2010 FIFA World Cup -- replaces Zanele Khanyile.
Khanyile has been reassigned within the SA Football Association (Safa) structures.
"She (Monyepao) brings along a wealth of experience in the team both from the technical and administrative point of view," said Safa chief executive, Robin Petersen.
"We want the players to concentrate on playing and nothing else. Lydia is highly qualified for the job having been there and seen it all we could not have a better person."
Monyepao said she wanted to add value to the side that will be competing in the Olympic Games for the first time, when the sporting showpiece takes place in London later this year.
"As a former player, I am very honoured about this appointment and I hope to add value to this squad which I believe will do the nation proud in London," she said. Safa has also appointed SA Under-23 coach Shakes Mashaba as the team's technical advisor, working alongside coach Joseph Mkhonza.
Francisco Gonzalez, Bafana Bafana's physical trainer, will work with the team while Safa have also enlisted Amisco as Banyana's statistical and video analysis providers.
Banyana are currently holding a training camp in Cape Town and, are due to partake in the Cyprus 12-Nation tournament starting later next month.