Anxiety sensitivity (AS) has been linked to both pathological anxiety and substance use problems. We evaluated relations between AS and substance use situations among individuals with substance use disorders (SUDs) and concurrent DSM-IV anxiety disorders. We predicted that AS would be most strongly associated with substance use in situations involving negative emotions and interpersonal conflict in substance abusers with anxiety disorders. This group was compared to substance abusers with concurrent mood disorders and substance abusers without other disorders (N=88). AS was positively related to negative emotion situations substance use for substance abusers with anxiety disorders and for substance abusers without other disorders. Contrary to predictions, significant differences between these groups were not found. The relationship between AS and negative emotion situations substance use remained after controlling trait anxiety in a combined group (anxiety disorders and substance abuse only groups). AS did not predict substance use for participants with concurrent mood disorders. Identification of factors that place anxious patients at risk for substance use problems will have implications for treatment and for the prevention of this form of maladaptive coping.