PurposeThe construction of digital supply chains to integrate internal and external resources is becoming an important path for manufacturing enterprises to gain competitiveness. However, at present, research on the internal mechanisms of digital supply chain capabilities (DSCC) and enterprise sustainable competitive performance (ESCP) has not been sufficiently studied. Based on contextual ambidexterity theory, this study investigates whether DSCC could enable the realization of supply chain ambidexterity and further explains the mediating role of supply chain ambidexterity on DSCC and ESCP, and the boundary conditions of supply chain governance on supply chain ambidexterity and ESCP.Design/methodology/approachWith a survey data set of 232 Chinese manufacturing enterprises from different industries, the study empirically tests a moderated mediating model and conducts hierarchical linear modeling and bootstrap to test the study's hypotheses.FindingsThe results demonstrate that: (1) DSCC positively enhance ESCP; (2) supply chain ambidexterity, which can be regarded as a synergic ability of supply chain alignment and adaptability, partially mediates the positive relationship between DSCC and ESCP; and (3) supply chain governance such as incentive governance positively moderates the association between supply chain ambidexterity and ESCP, but there is no evidence that relational governance moderates their relationship.Originality/valueThis paper proposes a new interpretive perspective to understand digital supply chains. More importantly, it reveals the importance of DSCC in contributing toward supply chain ambidexterity and ESCP, and demonstrates the differential regulating action of incentive and relational governance on the association between supply chain ambidexterity and ESCP, with implications for both academics and practitioners.