The seven singles included in The Velvet Underground Singles 1966–69 comprise the four Velvets singles originally released in the U.S. on the Verve and MGM labels, plus an additional pair of singles that were prepared for release but never made it to the marketplace and a special radio-only promotional single. The singles feature alternate mono versions that differ in significant ways from the songs' better-known stereo album versions. For instance, the band's 1966 debut single "All Tomorrow's Parties" appears here in a special mono edit that amplifies the song's melodic beauty and sonic tension, and a mono mix of their sophomore single "Sunday Morning" emphasizes the song's haunting quality. Meanwhile, the mono single version of "White Light/White Heat" exemplifies the vintage Velvets' stark, distortion-laden fury, while a mono edit of "What Goes On" accentuates that song's inherent pop jangle.
The Velvet Underground Singles 1966–69 also includes two unissued singles, one with a never-released pairing of "White Light/White Heat" backed by "I Heard Her Call My Name," and the other with "Temptation Inside Your Heart" and "Stephanie Says," recorded in the waning days of the band's classic Reed/Cale/Morrison/Tucker lineup and unheard by the public for nearly two decades thereafter. The set's seventh single is a reproduction of a vintage promotional disc, a two-and-a-half minute radio spot promoting the band's eponymous third album and featuring legendary disc jockey Bill "Rosko" Mercer, with excerpts from "I’m Set Free," "What Goes On" and "Beginning to See the Light," as well as a picture sleeve with an un-airbrushed variation on the album's iconic cover art.