The main challenge of interventions in penitentiary institutions is the re-education and reintegration of inmates, i.e., that inmates have the intention and ability to live law-abiding lives. Therefore, an increase in self-control or, on the contrary, the decrease or elimination of impulsive versus compulsive behaviors becomes necessary. This study aimed to evaluate the role of impulsivity versus compulsivity in treatment adherence in the prison population. The study included 134 men from the Penitentiary Center of Granada who were divided into two groups. Group 1 was considered treatment adherent, and Group 2 was considered non-adherent to treatment. The following instruments were used: Symptom Inventory (SCL-90-R), Addiction Severity Index (EuropASI), Impulsivity Scale (UPPS-P), and Compulsive Belief Questionnaire (OBQ-44). Statistically significant differences were found in impulsivity in the dimensions of negative urgency, sensation seeking, and positive urgency, with higher scores in all cases for the non-adherent group than for the adherent group. We also found statistically significant differences in responsibility/inhibition, perfectionism/uncertainty, and importance/control, with higher scores for the non-adherent group compared to the adherent group. Treatment adherence is inversely related to impulsive and compulsive behaviors.