This work studies the effect of the temperature in the solvothermal synthesis of CdS modified with Ag (Ag-CdS) over both the structure of CdS and the chemical state of the Ag species. The increase in the solvothermal temperature produces the evolution of the CdS nanostructures from nanoparticles of low crystallinity in coexistence with small nanocrystals with strong confinement effect to the formation of highly crystalline nanorods. The Ag species also change with the solvothermal temperature from Ag2S species, formed at low temperature, to metallic species as the temperature increases. The photoactivity of the Ag-CdS samples is the result of the combination of three factors: crystallinity of the CdS structures, existence of small nanocrystals with strong confinement effect and the presence of segregated Ag2S species. The Ag-CdS sample prepared at 120 °C shows the better efficiency for hydrogen production because it achieves the better combination of the aforementioned factors