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The present study investigated the extent to which inter-personal skills, personality, and emotional intelligence (EI) were related to the extent of usage of the Internet, as measured with the Internet Addiction Scale, on a sample of undergraduates. EI was assessed by performance measures derived from the identification and labeling of emotions as shown in pictures of facial expressions, and as interpreted from descriptions of social episodes. Use of the Internet was related to loneliness and adherence to idiosyncratic values (strong effects), and also to poorer balance between work and leisure and emotional intelligence (weaker effects). Big Five personality dimensions were also included in the study. No link was found between personality and usage of the Internet. Results suggest that frequent users tend to be lonely, to have deviant values, and to some extent to lack the emotional and social skills characteristic of high EI.