Penne, 30, is riding a three-fight win streak, while Waterson won each of her last four.
The inaugural flyweight championship will be featured as the co-main event, as Barb Honchak (7-2) fights Vanessa Porto (15-5).
Hyatt looks to get back in the win column following her Invicta FC 4 loss to Carla Esparza, while Cive hopes to extend her win-streak to six. Hyatt instantly became one of the hottest up-and-coming stars in female MMA with her gritty performance against Esparza, so her tilt against Cive has "Fight of the Night" written all over it.
In other main card action, former Strikeforce women's bantamweight champion Sarah Kaufman is set to make her Invicta FC debut, but her opponent has not yet been formally announced.
Invicta FC vet Leslie Smith was slated to fight Kaufman at Invicta FC 4, so there's a strong possibility that they will meet inside the cage in April.
Kaufman hasn't fought since losing to Ronda Rousey in Aug. 2012.
Invicta FC President Shannon Knapp said on Facebook on Feb. 4 that the Invicta FC 5 location, date and full fight card will be revealed this week.
"It is going to be a great week! Lots of exciting announcements coming up!" Knapp wrote. "Invicta FC #5 location, date, full fight card with 14 fights and we are welcoming a lot of new athletes to the Invicta FC family. Good stuff!"
Rose Namajunas (1-0), Veronica Rothenhausler (1-0) and Nicdali Rivera-Calanoc are the latest fighters rumored to appear on the Invicta FC 5 card, while Tecia "Tiny Tornado" Torres most likely will not be fighting at the event.
Torres is preparing to make her Muay Thai debut, so her busy training regimen would make it too difficult to also fight at Invicta FC 5.
Invicta FC 5 will likely be held on Apr. 6 in Missouri, not on Apr. 13 in Irvine, Calif., as had been originally reported.