The thermal and electrical properties of organic semiconductor are playing critical roles in the device applications especially on the devices with large area. Although the effect may be minor in a single device like field effect transistors, the unwanted waste heat would cause much more severe problems in large-scale devices as the power density will go up significantly. The waste heat would lead to performance degradation or even failure of the devices, and thus a more detailed study on the thermal conductivity and carrier mobility of the organic thin film would be beneficial to predict the limits of the device or design a thermally stable device. Here we explore the thermal annealing effect on the thermal and electrical properties of the small molecule organic semiconductor, dinaphtho[2,3-b:2’,3’-f]thieno[3,2-b]thiophene (DNTT). After the post deposition thermal annealing, the grain size of the film increases and in-plane crystallinity improves while cross-plane crystallinity keeps relatively constant. We demonstrated the cross-plane thermal conductivity is independent of the thermal annealing temperature and high annealing temperature will reduce the space-charge-limited current (SCLC) mobility. When the annealing temperature increase from 24 °C to 140 °C, the field effect mobility shows a gradual increase while the threshold voltage shifts from positive to negative. The different dependence of the SCLC mobility and field effect mobility on the annealing temperature suggest the improvement of the film crystallinity after thermal annealing is not the only dominating effect. Our investigation provides the constructive information to tune the thermal and electrical properties of organic semiconductors.