The purpose of this study was to assess psychometric properties of the CEAT-VIH (“Cuestionario para la Evaluación de la Adhesión al Tratamiento Antirretroviral en Personas con Infección por VIH y Sida” in the original) questionnaire applied to 652 HIV+ adult Colombian population and identify perceived psychological barriers to self-reported adherence. Questionnaire items analysis showed that most items were expectedly skewed toward reporting adherence. Corrected homogeneity index for the 20 items varied between 0.08 and 0.70. However, none of the items would considerably improve the reliability if deleted. Total score on CEAT-VIH ranged from 42 to 89 (median 83, mean 80.5, SD 8.1). Mean adherence scores varied across cities. No floor (0%) or ceiling (0.8%) effects was observed for the CEAT-VIH adherence score, and 85% of respondents scored 87 or below (cutoff score ≥ 87 = strict adherence). The instrument showed good reliability (Cronbach’s α = .86) and evidences of criterion-related validity. Adherence behaviors seemed to be particularly at risk when the patients felt physically better or worse or emotionally distressed, if they perceived adherence as difficult and requiring time and effort, if they had less confidence in their ability to comply with medications, if they felt less satisfied with their treatment and consultant, if they had low information about the treatment and if they experienced burden side effects. The application of the CEAT-VIH to Colombian HIV+ adult population shows to be useful, reliable, and valid, and it allows recommending the instrument for research and clinical practice assessment in this population.