In this study, we show the extent of interfacial behaviour in the mechanical performance of thermoplastic polyurethane elastomer (TPU)/acrylonitrile butadiene styrene (ABS) composite material manufactured using droplet-based additive manufacturing. Both the interface orientation and the interface strength are varied during the processing. Prior to tensile experiments, X-ray micro-tomography imaging is undertaken to obtain the microstructural arrangement of polymer droplets in the part. Tensile loading is performed simultaneously with digital image acquisition to reveal the extent of strain localization using a digital image correlation approach. The experiments are performed up to the failure of the specimens. Finite element computation based on 3D imaging of the ABS/TPU composite is considered to predict the role of the interface as well as the defect influence on the tensile performance. The experimental results show a major connectivity of the process-generated porosity and a distinct morphology of the ABS/TPU interface. The predictions demonstrate that, despite the limited amount of porosity, their connectivity plays a significant role in triggering damage initiation and growth up to the failure of the composite material.