As firms seek multiple pathways for growth and competitiveness, effectively commercialising internal technologies leads to outbound open innovation. Both absorptive capacity and desorptive capacity are knowledge management capabilities crucial for open innovation. While absorptive capacity is well explored by researchers, studies around desorptive capacity are scarce. This study addresses recent calls for a more in‐depth exploration of the role of desorptive capacity, which is still in its cradle stage. Firstly, a synthesis of the literature on desorptive capacity was conducted from related fields like open innovation, external knowledge exploitation, technology transfer, technology commercialisation, and so on. Then, based on the synthesis, a theoretical framework was formulated to explain the role of desorptive capacity in enabling firms to identify, transfer and commercialise their internal technology outside their firm boundaries. Testable propositions were formulated around the role, antecedents and consequences of desorptive capacity. The findings were discussed along with a comparison between absorptive and desorptive capacities. The implications for both theory and practice are listed. The paper concludes by enumerating the limitations of this study and offering future research directions.