Stimulus equivalence is a behavioral phenomenon that has been related to complex human behavior (e.g., remembering, cognitive functioning, and symbolic behavior). As a rule, people diagnosed with severe mental disorders (e.g., schizophrenia, bipolar disorder) that exhibit delusional and hallucinatory behavior, and disorganized speech have shown cognitive impairment (e.g., processing speed, reasoning/problem solving). Not enough research has analyzed the stimulus equivalence performance in this population. This study aims to investigate the stimulus equivalence performance in adults diagnosed with severe mental disorders. In particular, this study analyzes the many-to-one (MTO) and one-to-many (OTM) training structures effects, and the simultaneous (SIM) and the simple-to-complex (STC) training and testing protocol effects on equivalence class formation in this population. To achieve it, we analyzed the behavior of 18 participants diagnosed with severe mental disorders in three different conditions (Condition 1 OTM/SIM; 2 MTO/SIM; and 3 MTO/STC). Behavior consistent with stimulus equivalence was found in 11 out of 13 participants who had finished the study (5 participants decided to leave before completing the tasks). STC yielded better results than the SIM protocol. No differences were found between MTO and OTM training structures. Implications and suggestions for further research have been discussed.