Born in Kansas City, Missouri, James graduated from the University of Missouri-Kansas City with a bachelor of arts degree in theater. Soon after, she had her first break on television, playing the recurring role of Ella Payne on the Nickelodeon sitcom Kenan & Kel. It aired for four seasons from 1996 to 2000. After that series ended, she made several appearances in other series and guest-starred in the series The Parkers and Moesha. She received her big break when she was cast as Dr. Stacy Warner in the BET comedy-drama series The Game.
Outside of acting, James is also an accomplished writer. She has written articles on her website and has created several podcasts. She is the founder of the lifestyle and fashion brand, "Chic Charmayne". She has also authored a memoir titled "Not That Funny".