This paper investigates the association between structural aspects of interorganizational collaborations and psychosocial processes of trust and identification in Inter-organizational Governing Teams (IGT). A first study used secondary data on 240 interfirm networks. Size of the alliance, presence of a network manager and the previous collaboration vs. recent foundation of the collaboration, were used as grouping variables in a cluster analysis. Results show five types of interfirm alliances. In a second study, members of twenty interorganizational governing teams (67 managers/entrepreneurs), answered a questionnaire on psychosocial variables. Results show that IGTs of larger and recently established interfirm networks present lower levels of interorganizational trust and of trust in team, in comparison to IGTs of networks with lower number of partners or with a previous history of collaboration.