This chapter begins with a literature review of small and medium-sized enterprises (SME) internationalization, as well as strategic alliances in general and asymmetrical alliances in particular. It discusses the main constraints SMEs face in their internationalization processes, as well as the role of inter-organizational relationships—and particularly asymmetric alliances—in addressing these constraints. Asymmetric alliances are generally considered as cooperative operations between companies of different sizes, and especially between SMEs and MNCs. The research methodology selected is a qualitative, multiple case study, a methodological choice guided by our goal of understanding and explaining how asymmetric strategic alliances impact SMEs’ internationalization processes. The chapter concludes by discussing our results and highlighting the implications of our research findings, the limitations of the research, and possible extensions of the research area for future studies. Among the internationalization options available to SMEs, inter-organizational relationships are widely recognized as essential, as they provide SMEs with the necessary information and resources to access new markets.