The lead single is the title track "Love After War", released on October 11, 2011. It officially impacted U.S. Urban radio on October 18, 2011. The music video was released on November 21, 2011. It impacted Smooth Jazz radio on November 22, 2011.
The second single, "Pretty Lil' Heart" featuring Lil Wayne, was released on November 8, 2011. It impacted Urban and Urban Mainstream radio on November 21 and November 22, 2011. The music video was released on March 2, 2012.
"All Tied Up" was released as the third single. It impacted Urban Adult Contemporary radio on April 10, 2012. The music video was released on June 7, 2012.
Allmusic editor Andy Kellman commented that "Thicke has settled into a suave, and even more swashbuckling, sound" and wrote of its second half of seductive ballads, "They don’t offer much in the way of development from Thicke’s recent past [...] but they should get the job done."Slant Magazine's Matthew Cole "Thicke spends most of Love After War singing in full voice, with mixed results", adding that "since Love After War stretches its seduction routine out for 17 tracks, the weight of its throwaway songs starts to add up." Nate Chinen of The New York Times wrote that Thicke "ask[s] you to admire his tasteful slickness without delving much deeper than the surface."Rolling Stone writer Jody Rosen stated, "Thicke spends a lot of time pondering romantic turmoil, but he's at his best when he reverts to classic loverman form: squeezing gentle bossa nova chords on his acoustic guitar, and letting his feathery upper register do the dirty work."
Kyle Anderson of Entertainment Weekly complimented Thicke's "creamy voice" and stated, "At 17 tracks, his loverman act grows a little exhausting, but perhaps he's just giving wannabe lotharios a seduction time frame to aspire to." Elysa Gardner of USA Today wrote that the album "can find him self-consciously smooth at times, suggesting too much artful foreplay. Still, this is a consistent showcase for his dextrous singing, which evokes pop/R&B icons from Marvin Gaye to Michael McDonald," complimenting "his ability to serve old-school textures with a fresh and not-too-shiny finish."