Despite the fact that vocational interests constitute one of the main variables that influence decision-making, their study does not begin until ages that could require late hours, such as Secondary Education. In order to alleviate this deficit, a longitudinal study was carried out, whose main objective was to analyse to what extent a networked learning environment contributes to a better behaviour of primary school students towards their vocational interests. An educational program was developed and implemented based on the international R&D e-Cultures Project. Spain, Portugal and several Latin American countries participated in the research. The evaluation of the program was carried out using a quasi-experimental pretest-posttest design in which an ad hoc questionnaire was applied to collect the data. The results showed a stronger career decision in boys (as opposed to girls). On the other hand, vocational interests were less related to the country of residence. It is concluded that vocational guidance, working collaboratively in a networked learning environment with an intercultural perspective, enhances the decision-making process and definition of professional goals, contributing to the teaching of science in primary school students.