In order to utilize the synergistic effect between a conductive polymer and an inorganic semiconductor to efficaciously enhance charge transfer and solve the problem of unsatisfactory performance of a single photocatalyst, thiophene (Th) was polymerized on the Cd0.5Zn0.5S nanoparticle surface to prepare a conductive polymer-inorganic polythiophene/Cd0.5Zn0.5S (PTh/CZS) heterostructrue through a simple in situ oxidation polymerization for the first time. The as-prepared PTh/CZS heterostructures significantly improved photocatalytic TCH degradation and hydrogen production activities. Especially, the 15PTh/CZS sample exhibited the optimal hydrogen production rate (18.45 mmol g-1 h-1), which was 2.51 times higher than pure Cd0.5Zn0.5S nanoparticles. In addition, 15PTh/CZS also showed very fast and efficient photodegradation ability for degrading 88% of TCH in 25 min. Moreover, the degradation rate (0.06229 min-1) was five times more than that of Cd0.5Zn0.5S. The π-π* transition characteristics, high optical absorption coefficient, wide absorption wavelength of PTh, the tight contact interface, and synergistic effect of PTh and Cd0.5Zn0.5S efficiently boosted charge transfer rate and increased the light absorption of PTh/CZS photocatalysts, which greatly enhanced the photocatalytic abilities. Besides, the mechanism of improved photocatalytic activities for TCH degradation and H2 production was also carefully proposed. Undoubtedly, this work would provide new insights into coupling conductive polymers to inorganic photocatalysts for achieving multifunctional applications in the field of photocatalysis.