The series, which also features Eddie Murphy and Jose Canseco's exes, will premiere this summer with 10 hourlong episodes.
The unscripted show, which has been granted a 10-episode order by the pop culture-themed network, stars Mayte Garcia (formerly Mrs. Prince), Andrea Kelly (formerly Mrs. R. Kelly), Sheree Fletcher (formerly Mrs. Will Smith), Nicole Murphy (formerly Mrs. Eddie Murphy) and Jessica Canseco (formerly Mrs. Jose Canseco).
"These extraordinarily strong women adjusted to and endured a lot while their ex-spouses won fame and fortune defining pop culture for that moment," said Jeff Olde, executive vp original programming and production at VH1.
"Now these women must reinvent themselves again, stepping out of the long shadows cast by their famous husbands and supporting each other as they define the next stage of their lives -- this time on their own terms," he added.
The tentatively titled "Hollywood Exes" sets out to peel back the curtain on Cinderella tales gone wrong. The five women have been friends for several years and are looking to make a name for themselves outside of their bold-face exes.