We investigated the thermal conductivity of materials based on pyrolysis temperature, filler loading, filler size, and type of biomass feedstock. Hemp stalk and switchgrass were pyrolyzed at 450, 550, and 650 °C and crushed into 50, 75, and 100 μm particle sizes. Biocarbon fillers (10, 15, and 20 wt %) were added to the bioepoxy polymer matrix. The study showed increased filler loading and particle size increased thermal conductivity�the biocomposite samples with 20 wt % filler loading of 100 μm particle size of the biocarbon obtained at 650 °C showed the maximum thermal conductivity in both hemp biocarbon-filled composites (0.59 W•m −1 •K −1 ) and switchgrass-filled composites (0.58 W•m −1 •K −1 ) with the highest flame time. Biocarbon in biofiber-reinforced polymer composites can improve thermal conductivity and extend the flame time. These findings significantly contribute to developing hemp-based bioepoxy composite materials for thermal applications in various fields. These include insulating materials for buildings and thermal management systems, energy-efficient applications, and help in material selection and product design with a positive environmental impact.