To explore the thermal effect of interfacial friction at the nano/microscale, a solid-solid contact model of a rough surface with a single peak was established to research single-crystal Fe. The friction characteristics, stress distributions, temperature changes, and energy changes under different indentation depths and lattice orientations during the shearing process were analyzed. From the perspective of temperature and energy, the mechanism of the thermal effect was revealed. The relationship between the friction force, temperature, and energy at the atomic scale was clarified. The results showed that the temperature of the asperities gradually increased during the shearing process, and a stress concentration formed in the shearing zone. After contact, the asperities had undergone unrecoverable plastic deformation, and there was wear at the contact interface accompanied by the loss of atoms from the asperity. At each indentation depth, as the rotation angle of the crystal increased, the friction force, average temperature, and the sum of the changes in thermal kinetic and thermal potential energy all first increased and then decreased; the trends of the three parameters changing with the rotation angle of the crystal were consistent. The average decreases in the friction force, average temperature, and the sum of the changes in thermal kinetic and thermal potential energy were 52.47%, 30.91%, and 56.75%, respectively, for a crystal structure with a rotation angle of 45° compared to a crystal structure with a rotation angle of 0°. The methods used in this study provide a reference for the design of frictional pairs and the reduction of the thermal effect of interfacial friction.