TV Line claims that Wolfe will replace Amanda Loncar, who was previously cast in the project.
The comedy focuses on a group of people as they try to negotiate love and romance in New York City.
Wolfe is thought to have landed the role of Holly, who is married to Tim (Ryan Hansen). The project will also star Sean Maguire as Tim's brother Blake and Stella Maeve as his sister Maddie. Meanwhile, Kate Cho will play Blake's ex-wife Kate.
Wolfe plays Kirsten in Cougar Town and also starred as Jill in 100 Questions. She has had guest roles in shows including Eastbound & Down, How I Met Your Mother and Reaper, and worked on movies such as Hot Tub Time Machine and 17 Again.
Lovelives is in contention for NBC's 2011-2012 season.