Notwithstanding the contemporary relevance of alliance strategies for SME internationalization, especially in the case of uncertain business environments, few studies have investigated human resource issues in the context of SMEs prior to alliance formation. Even more scarce are studies looking at the impact of a manager/entrepreneur’s characteristics on pre-alliance formation, despite recognition of the expected crucial role of the entrepreneur in this context and of the strong connection between an entrepreneur and their SME. Drawing on international entrepreneurship theory and empirical observations from an exploratory study, we propose a post-hoc conceptual model. The exploratory empirical part of our study employs a sample of entrepreneurs from biotechnology SMEs in the United Kingdom and Germany intending to ally in a large emerging market (i.e., Brazil). Our empirical observations suggest an anomalous (at first glance) negative association between the entrepreneur’s level of higher education (a construct at individual level) and the attractiveness of the SME as a partner-firm vis-à-vis alliance formation (a construct at firm level). Our post-hoc model emphasises the role of practical experience and the corresponding levels of international entrepreneurial orientation as theorised variables mediating the observed empirical relationship. We develop theoretical propositions, and suggest practical implications and future research directions.