Relapse is common during the process of giving up smoking. The aim of the present study is to explore the relapse situations, according to Marlatt’s relapse taxonomy, in a sample of 428 smokers (43.9% men and 56.1% women) who participated in a cognitive-behavior psychological treatment for quitting smoking. At the end of the treatment, 221 participants were abstinent, of whom 119 (41.2% men and 58.8% women) relapsed in the course of the 12-month follow-up, the majority in the first 3 months (69.74%). Most of the relapses were attributed to intrapersonal and environmental determinants (61.33%), the most common of which were “coping with negative emotional states” (38.65%), followed by “giving in to temptations or urges” (9.24%) and “testing personal control” (8.40%). Interpersonal determinants occurred in 38.66% of relapses, this percentage being made up mostly of “social pressure”, which was the relapse situation in 34.46% of all relapses. These results, similar to those of Marlatt’s original studies and others, contribute to improving our knowledge of the relapse situations process, with a view to interventions that may help to avoid it.