Impulsivity is predominant among users of several drugs of abuse including alcohol, cocaine, and amphetamines, and it is considered a risk factor for later development of alcohol and substance abuse and dependence. However, there is little consensus on how impulsivity should be defined and measured, and there are few studies on the relationship between separate dimensions of impulsivity and substance dependence. We used a multidimensional measure of impulsivity (the UPPS scale) to examine differences between 36 individuals with substance dependence (ISD) and 36 drug-free controls on the dimensions of urgency, lack of premeditation, lack of perseverance, and sensation seeking. In addition, we examined which dimensions of impulsivity better predicted addiction-related problems as measured with the addiction severity index. Results revealed that ISD show high scores on dimensions of urgency, lack of perseverance, and lack of premeditation (effect sizes ranging from 1.10 to 1.96), but not on sensation seeking. Among the different impulsivity dimensions, urgency was the best predictor of severity of medical, employment, alcohol, drug, family/social, legal and psychiatric problems in ISD, explaining 13–48% of the total variance of these indices. Furthermore, urgency scores alone correctly classified 83% of the participants in the ISD group. Urgency is characterized by a tendency to act impulsively in response to negative emotional states. Thus, our results could have important implications for novel treatment approaches for substance dependence focused on emotional regulation.