It is well established that methadone maintenance (MM) reduces but does not eliminate the self-administration of other illicit drugs. For those on MM, there is considerable variation in consumption patterns, route of heroin administration, additional non-opioid substances routinely administered and the clinical disorders associated with these patterns of use. While there is a large literature base documenting these phenomena, studies have been almost exclusively descriptive in nature, with little attempt to develop a theoretical model in which to understand such use. In the following thesis, a model proposed by Gray was tested, the Reinforcement Sensitivity Theory (RST). This biopsychosocial model broadly describes two action tendencies; approach (Behavioural Activation System) and avoidance or withdrawal (Flight Fight Freeze System and the Behavioural Inhibition System). The model proposes that a heightened sensitivity to punishment underlies anxiety disorders. Conversely, a heightened sensitivity to rewarding stimuli may predispose some individuals to engage in highly rewarding behaviour and is associated with conduct disorder and antisocial personality disorder. According to the Joint Subsystems Hypothesis, these personality styles are mutually dependent, whereby BIS and BAS interact to influence reward mediated and punishment mediated behaviours. Based on Gray's model, this thesis tests whether opiate dependent individuals with heightened sensitivity to punishment are more likely to use anxiolytic drugs (such as benzodiazepines), and individuals with heightened reward sensitivity will show a preference for substances that have high reward potential (such as stimulants). At time one, the participant sample (N= 120) comprised 71 males (59%) and 49 females who were opioid dependent and recruitment took place over an eight-month period in two city opioid replacement clinics. A range of measures was administered to assess substance use, mood, anxiety and the personality dimensions of reward sensitivity and punishment sensitivity, with substance use again measured at three months. Results of the first study suggested that a large proportion of the variance was accounted for by personality within the models. A total of 98 participants (81%) participated in the 12-week follow-up study. Sensitivity to punishment and reward significantly predicted drug preference. Although psychopathology symptoms were not able to moderate the relationship between personality and drug use, anxiety symptoms negatively mediated the relationship between punishment sensitivity and anxiolytic use, whereby the relationship became non-significant. In contrast, sensitivity to reward remained the strongest predictor of amphetamine use over antisocial characteristics. Individual differences were not able to predict treatment retention nor susceptibility to relapse during a 12-week initiation to a MM programme.