Silver nanoparticles were loaded onto g-C3N4 (CN) with a nanoroll-type morphology (Ag/CN) synthesized using a co-polymerization method for highly selective conversion of toxic nitrobenzene to industrially-valuable aminobenzene. Scanning electron microscopy and high-resolution transmission electron microscopy (HRTEM) images of Ag/CN revealed the generation of the nanoroll-type morphology of CN. Additionally, HRTEM analysis provided direct evidence of the generation of a Schottky barrier between Ag and CN in the Ag/CN nanohybrid. Photoluminescence analysis and photocurrent measurements suggested that the introduction of Ag into CN could minimize charge recombination rates, enhancing the mobility of electrons and holes to the surface of the photocatalyst. Compared to pristine CN, Ag/CN displayed much higher ability in the photocatalytic reduction of nitrobenzene to aminobenzene, underscoring the importance of Ag deposition on CN. The enhanced photocatalytic performance and photocurrent generation were primarily ascribed to the Schottky junction formed at the Ag/CN interface, greater visible-light absorption efficiency, and improved charge separation associated with the nanoroll morphology of CN. Ag would act as an electron sink/trapping center, enhancing the charge separation, and also serve as a good co-catalyst. Overall, the synergistic effects of these features of Ag/CN improved the photocatalytic conversion of nitrobenzene to aminobenzene.