The exploitation of the stable and earth-abundant electrocatalyst with high catalytic activity remains a significant challenge for hydrogen evolution reaction. Being different from complex nanostructuring, this work focuses on a simple and feasible way to improve hydrogen evolution reaction performance via manipulation of intrinsic physical properties of the material. Herein, we present an interesting semiconductor-metal transition in ultrathin troilite FeS nanosheets triggered by near infrared radiation at near room temperature for the first time. The photogenerated metal-phase FeS nanosheets demonstrate intrinsically high catalytic activity and fast carrier transfer for hydrogen evolution reaction, leading to an overpotential of 142 mV at 10 mA cm and a lower Tafel slope of 36.9 mV per decade. Our findings provide new inspirations for the steering of electron transfer and designing new-type catalysts.