Exploiting the promise of nanocomposite oxides necessitates a detailed understanding of the dislocation structure at the interfaces, which governs diverse and technologically relevant properties. Here we report atomistic simulations demonstrating a strong dependence of the dislocation structure on the termination chemistry at the SrTiO 3 /MgO heterointerface. The SrO-and TiO 2 -terminated interfaces exhibit distinct nearest neighbour arrangements between cations and anions, leading to variations in local electrostatic interactions across the interface that ultimately dictate the dislocation structure. Networks of dislocations with different Burgers vectors and dislocation spacing characterize the two interfaces. These networks in turn influence the overall stability of and the behaviour of oxygen vacancies at the heterointerface, which will dictate vital properties such as mass transport at the interface. To date, the observed correlation between the dislocation structure and the termination chemistry at the interface has not been recognized, and offers novel avenues for fine-tuning oxide nanocomposites with enhanced functionalities.