This study aims to analyse the relationship between strategic alliances and organizational performance and determine whether intellectual capital plays a mediating role in that relationship. To do so, a quantitative study was chosen, with data being gathered through questionnaires directed to the management organs of Portuguese industrial technology‐based small and medium‐sized enterprises, from which 257 valid responses were received. The results obtained based on a structural model show that strategic alliances and intellectual capital stimulate the organizational performance of the SMEs studied. This evidence is very relevant, as in an increasingly globalized and competitive world, these two tools can become essential for this firm sector to be able to attain sustainable competitive advantages. Furthermore, the empirical evidence reveals that intellectual capital has a mediating effect on the relationship between strategic alliances and organizational performance, this finding being the main contribution of the study. Other implications for theory and practice will be presented.