Heart of a Woman was released during a period of James' career in which she parted from singing blues to experiment with country, jazz, and pop music, with mixed reception.

Guest musicians appearing on the album included: Mike Finnigan on organ, Red Holloway and Jimmy Zavala on tenor saxophone, and Lee Thornburg on multiple instruments.

Gene de Paul and Don Raye's "You Don't Know What Love Is" opens the album, followed by "Good Morning Heartache", written by Ervin Drake, Dan Fisher, and Irene Higginbotham.

[1] James' vocals on Duke Ellington and Paul Francis Webster's "I Got It Bad (and That Ain't Good)" are "barely audible" as she sings "...

[1] Mike Finnigan performs the Hammond organ solo on "A Sunday Kind of Love" and throughout the album, filling the gap between blues and jazz music.

PopMatters' review concluded that, given proper arrangements and material, James delivered jazz standards "with the same devastating power" demonstrated on past blues performances.

[2] PopMatters' review was positive overall, claiming James' rough voice made her appear to be "in tune with the woeful nature" of the songs, though it insisted that her cover of "Only Women Bleed" was a "miscalculation of major proportions".

[2] AllMusic's Stephen Thomas Erlewine called James one of the best blues performers of the twentieth century and wrote in his review of the album that "she still possesses an exceptionally strong voice, robust and filled with passion.