Human-robot collaboration (HRC) is effective to improve productivity in industrial fields, based on the robot's fast and precise work and the human's flexible skill. To facilitate the HRC system, the first priority is to ensure safety in the event of accidents, such as collisions between robots and humans. Therefore, a protective and collision-sensitive robot skin, named Gel-Skin is proposed to guarantee the safety in HRC. The Gel-Skin is composed of polyvinyl chloride (PVC) gel, which is a functional material with piezoresistive characteristics and impact absorption capability. In particular, the PVC gel has a distinctive piezoresistive property that the relation between mechanical pressure and electrical resistance is tunable depending on an applied voltage. When a voltage is applied to the PVC gel, the electrical charges are accumulated around the anode and it shows increased piezoresistive sensitivity. In this study, it is verified for the PVC gel to exhibit the 4.78 times higher sensitivity by simply applying a voltage. This novel physical phenomenon enables the Gel-Skin to detect the collision rapidly. Finally, the Gel-Skin is applicated to a real robot system and it is verified that the Gel-Skin can detect a collision and absorb impact to ensure safety. For safe human-robot collaboration (HRC), a protective and collision-sensitive robot skin is proposed. The developed robot skin, named Gel-Skin, is composed of polyvinyl chloride (PVC) gel, which is a functional material with impact absorption capability and tunable piezoresistive characteristics based on electrical charge-accumulation. The applicability of the Gel-Skin is verified with a real demonstration.image (c) 2024 WILEY-VCH GmbH