Natural paragenetic semiconducting minerals give important hints for fabricating stable and effective photocatalysts, which can be widely used in solar energy harvest and pollution control. To enhance the photoactivity of natural sphalerite (ZnS), needle-like nanocrystal MoS2 was loaded on sphalerite surface through a hydrothermal method, mimicking the intergrowth of molybdenite (MoS2) and sphalerite in nature. The resultant coupled MoS2/sphalerite exhibited a hydrogen evolution reaction (HER) potential at –0.35 V (vs. NHE), and showed obvious photoresponse under visible-light. The photodegradation rate of methyl orange (MO) over MoS2/sphalerite could reach 75% within 180 min. Compared to sphalerite, coupled MoS2/sphalerite had a higher photocurrent, more positive HER potential and 66% higher photodegradation rate. The enhanced photoactivity was attributed to the charge transfer from sphalerite to MoS2 and high electrons’ mobility on MoS2 layer.