The I-PACE model suggests that Internet-use disorders result from the interplay of individual vulnerabilities and cognitive and affective processes. As in substance use disorders, Pavlovian conditioning processes are attributed a key role. However, and despite progress in identifying individual vulnerabilities, factors influencing appetitive conditioning remain poorly understood. We therefore conducted a Pavlovian conditioning experiment in which individuals with risky as well as non-problematic use of either gaming or buying-shopping applications learned to associate different abstract stimuli with either gaming or buying-shopping. Regression analyses were used to identify individual characteristics influencing awareness of the experimental contingencies, speed of acquisition of awareness and the magnitude of the conditioned emotional responses regarding pleasantness and arousal ratings of the stimuli. Results demonstrated successful Pavlovian conditioning and an attentional bias towards reward-predicting cues. Awareness of the experimental contingencies was linked solely to cognitive abilities, while the speed of acquisition of awareness and the magnitude of conditioned responses was influenced by specific personality characteristics, experiences of compensation from using the application and severity of problematic use. Importantly, certain characteristics specifically predicted the magnitude of the conditioned response towards gaming, while others specifically predicted the response towards buying-shopping, highlighting differing vulnerabilities. These findings underscore the importance of targeted interventions and prevention strategies tailored to these specific vulnerability factors. Further implications and limitations are discussed.