In this work, we successfully synthesized a series of CdS-BiOCl/PAN composites by two-step method including electrospinning process and hydrothermal process. The CdS-BiOCl/PAN composites showed great photocatalytic performance and chemical stability for H-2 production under UV-vis light irradiation due to the synergistic effect among CdS, BiOCl and PAN. Meanwhile, the content of CdS in CdS-BiOCl/PAN composites plays an important role in photo-catalytic abilities. In addition, according to the analysis about the photocatalyst, the possible photocatalytic mechanism and synergistic interaction were further discussed.