E-commerce continues to develop as an important channel for consumer purchases. This explains the growing interest in determining the most important variables which affect online consumer behavior, especially perceived risk as a well-known behavioral deterrent. Previous studies have proved a negative influence of perceived risk on the intention to adopt e-commerce. However, depending on the type of product and the population investigated, results were often contradictory and this relationship was found to be stronger, weaker or even inconclusive. This led us to conclude that, besides direct influence factors, there could be moderating effects for the analyzed relationship. Moderators are qualitative or quantitative variables which modify a relationship, and affect the direction and/or strength of that relationship between an independent and a dependant variable. The purpose of our research was to investigate potential moderator variables which could change the relationship between perceived risk and the intention to buy online. We used three observable variables – gender, experience in using the Internet and experience with online shopping – and three latent, psychological variables – fear of uncertainty, trust in e-commerce and materialism. The research consisted of a survey conducted on a sample of 481 business students, followed by a Structural Equation Modeling approach. Although no moderation effect was proved, partly due to the homogeneity of the investigated pilot population, fear of uncertainty and trust in e-commerce were found to be antecedents of perceived risk in e-commerce, making perceived risk a mediator between these two variables and the intention to buy online.