High-temperature and high-pressure post-processing applied to sintered thermoelectric materials can create nanoscale defects, thereby enhancing their thermoelectric performance. Here, we investigate the effect of hot isostatic pressing (HIP) as a post-processing treatment on the thermoelectric properties of p-type Bi0.5Sb1.5Te3.0 compounds sintered via spark plasma sintering. The sample post-processed via HIP maintains its electronic transport properties despite the reduced microstructural texturing. Moreover, lattice thermal conductivity is significantly reduced owing to activated phonon scattering, which can be attributed to the nanoscale defects created during HIP, resulting in an ~18% increase in peak zT value, which reaches ~1.43 at 100°C. This study validates that HIP enhances the thermoelectric performance by controlling the thermal transport without having any detrimental effects on the electronic transport properties of thermoelectric materials.