Thermal infrared cameras sense the temperature information of sensed scenes. With the development of UASs (Unmanned Aircraft Systems), thermal infrared cameras can now be carried on a quadcopter UAV (Unmanned Aircraft Vehicle) to appropriately collect high-resolution thermal images for volcanic geothermal monitoring in a local area. Therefore, the quadcopter UAS used to acquire thermal images for volcanic geothermal monitoring has been developed in Taiwan as part of this study to overcome the difficult terrain with highly variable topography and extreme environmental conditions. An XM6 thermal infrared camera was employed in this thermal image collection system. The Trimble BD970 GNSS (Global Navigation Satellite System) OEM (Original Equipment Manufacturer) board was also carried on the quadcopter UAV to gather dual-frequency GNSS observations in order to determine the flying trajectory data by using the Post-Processed Kinematic (PPK) technique; this will be used to establish the position and orientation of collected thermal images with less ground control points (GCPs). The digital surface model (DSM) and thermal orthoimages were then produced from collected thermal images. Tests conducted in the Hsiaoyukeng area of Taiwan's Yangmingshan National Park show that the difference between produced DSM and airborne LIDAR (Light Detection and Ranging) data are about 37% between -1 m and 1 m, and 66% between -2 m and 2 m in the area surrounded by GCPs. As the accuracy of thermal orthoimages is about 1.78 m, it is deemed sufficient for volcanic geothermal monitoring. In addition, the thermal orthoimages show some phenomena not only more globally than do the traditional methods for volcanic geothermal monitoring, but they also show that the developed system can be further employed in Taiwan in the future.