The practice of harvesting vibration energy from machine tools, windmill blades, etc., and converting it into electric energy to power low-power electronic circuits has attracted wide attention from experts and scholars. Abundant vibrations that exist in the moving vehicle can be harvested to power sensors in tire pressure monitoring. In this paper, for the first time, a device is proposed to harvest the rotational vibration energy with the iron-gallium alloy (magnetostrictive material) as the core material. Such a device utilizes the coupling characteristics of Villarreal effect and Faraday electromagnetic effect to convert the vibration energy generated by the moving vehicle into electric energy. Upon completion of the design of the magnetostrictive rotational vibration energy harvester, the influence law of key factors, including substrate material, substrate size, and pre-magnetization field arrangement on the harvesting capability of the device, was studied in detail through experiments. An electric motor and vibration exciter were used to apply varied excitation forms to the harvester, and the output patterns of the harvester under conditions of wheel rotation, road bumps, and random vibration were fully analyzed. In addition, the correlation between the deformation of the cantilever beam and harvester performance was also investigated. The results have shown that at the acceleration of 9.6 g and the rotational speed of 90 r/min, the harvester can reach the output voltage of 1.22 V. Consequently, it demonstrates the feasibility of employing the magnetostrictive harvester to gather rotational vibration energy and provides theoretical guidance for further and deeper research on the harvester.