NbHfTiVC0.1 refractory high-entropy alloy (RHEA) exhibits excellent comprehensive mechanical properties and demonstrates great potential for applications. However, the mechanical properties need to be improved further. In this work, hot rolling on NbHfTiVC0.1 RHEA at temperatures of 650 °C, 850 °C, and 1050 °C, with total reductions of up to 30%, 50%, 70%, and 80%, was conducted. The microstructure and mechanical property evolution of the samples were further investigated. The hot-rolled samples at 650 °C and 850 °C exhibit a composition consisting of BCC, carbide, and Laves phases, whereas the samples rolled at 1050 °C only consist of BCC and carbide phases. The 650-80 sample displays the highest ultimate tensile strength (1354 MPa), and the 1050-80 sample demonstrates the highest elongation (16%). The highest strength observed in the 650 °C-80% sample can be attributed to the presence of fractured and refined carbides, fine-grains, and the hindrance of dislocation slip by the fine Laves phase. At a higher rolling temperature (1050 °C), the Laves phase disappears, resulting in a reduction in strength but an increase in plasticity. Furthermore, the dislocation slipping mechanism within the BCC matrix also contributes positively to plastic deformation, leading to a notable increase in ductility for the 1050 °C-80% sample. These research findings provide valuable insights into enhancing the strength and ductility simultaneously of NbHfTiVC0.1 RHEA through hot rolling.