Ag/CdS heterostructural materials were successfully synthesized by ultrasound-assisted polyols and hydrothermal method. Under hydrothermal condition, thiourea adsorbed on Ag nanowires releases S2− ions, which react with vicinal Cd2+ ions to form CdS clusters on Ag nanowires. Thereafter, the Ag/CdS composites grow into core–shell structure through CdS aggregation, Ostwald ripening, and preferential growth. The obtained core–shell structures and morphologies were investigated by XRD, SEM, and TEM; the experimental results indicate that the composites are composed of Ag nanowires serving as the core and CdS particles as the shell. The photocatalytic property of Ag/CdS core–shell materials was then investigated in detail. Comparing studies on the degradation of methylene blue were employed by using pure CdS, pure Ag, and Ag/CdS composites, respectively. The results show that the Ag/CdS composites possess higher photocatalytic degradation efficiency. Moreover, the Ag/CdS composites show improved stability, and the photocatalytic activity remains almost unchanged after four recycles. The enhanced photocatalytic effect for Ag/CdS composites is mainly attributed to the photogenerated electron transfer from CdS to Ag nanowire, while photogenerated holes still remain in CdS's valence band. Consequently, the effective separation of photogenerated electrons and holes and the resulting OH radicals improve the photocatalytic efficiency of Ag/CdS composites greatly.