Entrepreneurial intention (EI) is attracting research interest as a valid predictor of actual entrepreneurial activity, and a growing number of articles are approaching the subject both from theoretical and experimental perspectives. Motivation is considered the major driver of EIs. However, entrepreneurial barriers may hinder the formation of EIs and even cancel the realization of EIs into entrepreneurial activity. The constraints perceived by the prospective entrepreneurs (e.g., students) and the motives forming their intentions, analyzed in the literature, up to now, deliver some disparate findings about the significance and the relative power of the effects. The need for a unified instrument for the systematic investigation of the impact of barriers and motives on EIs is imperative. On the other hand, research on the EIs of students in the field of information technology (IT) is very rare, although the field consists a fertile ground for entrepreneurial activity and innovation. In order to fill this gap, a structured questionnaire was used to reveal the perceptions of entrepreneurial barriers and motivation, in a sample of 174 tertiary IT students. The data were subjected to statistical regression in order to identify causal relations between the barriers, motives, and EIs. The results indicated that the lack of entrepreneurial knowledge and skills have a major impact on EIs of students. On the contrary, self-motivation towards entrepreneurship acts as an antidote. Finally, the differences in the perception of barriers and motivation, between the two genders and role model groups, were also examined. The findings have valuable implications for educators in the IT field, due to the opportunities expected, in the context of Industry 4.0. Additionally, there are useful implications for policy makers, due to the ongoing economic crisis.