Identifying the processes by which environmental stimuli can come to influence drug use is important for developing more efficacious interventions. This study investigated derived relational responding and the transfer of differential conditioned effects of environmental stimuli paired with “smoked” cocaine in accordance with the relations of symmetry, transitivity, and equivalence using Heart Rate as the measure of conditioning among 12 adults with significant histories of cocaine use. Match-to-sample (MTS) procedures were used to test for emergent relations among two four-member stimulus groupings. One member of a group was then paired with 25 -mg of smoked cocaine and one member of the other group was paired with 0 -mg of smoked cocaine. Ten participants completed the MTS protocol: four participants demonstrated two four-member equivalence classes, three participants demonstrated two three-member equivalence classes, and two participants demonstrated symmetry only. One participant demonstrated no derived relations. Differential respondent elicited changes in HR was demonstrated in the presence of stimuli paired with smoked cocaine among four of the six participants completing the conditioning phase; all four of the participants demonstrated a bidirectional transfer of these functions in accordance with symmetry. Transfer was not reliably demonstrated in accordance with transitive or equivalence relations. The results suggest that respondent elicitation in the context of drug use may be a function of both direct conditioning and derived relational processes. These findings have implications for studying and understanding the processes by which stimuli in the natural ecology can set the occasion for cocaine use and developing cocaine use disorder.