Advances in flexible and multifunctional electronic devices have enabled the realization of sophisticated skin for robotics applications. In this paper, a large-scale, flexible and self-powered tactile sensing array (TSA) for sensitive robot skin is demonstrated based on the triboelectric effect. The device, with 4 × 4 sensing units, was composed of a top triboelectric polyethylene terephthalate (PET) layer, a bottom triboelectric copper (Cu) layer and a bottom PET substrate. A low-cost roll-to-roll ultraviolet embossing fabrication process was induced to pattern the large-scale top PET film with microstructures for high-output performance. The working mechanism and output performance of the triboelectric TSA were demonstrated and characterized, exhibiting good stability and high sensitivity. By integrating a tactile feedback system, the large-scale TSA, acting as intelligent skin for an industrial robot, was able to realize emergency avoidance and safety stop for various unknown obstacles under various working conditions. The system also has good real-time performance. By using a large-scale roll-to-roll fabrication method, this work pushes forward a significant step to self-powered triboelectric TSA and its potential applications in intelligent robot skin.