Orthorhombic Ag8SnS6 photoelectrodes are prepared on various substrates via reactive sulfurization using the radio-frequency magnetron sputtering of silver-tin metal precursors. Evaluations of the photoelectrochemical performances of Ag8SnS6 photoelectrodes with various levels of silver content are carried out in various aqueous solutions. X-ray diffraction patterns and Hall measurements of samples after a three-stage sulfurization process show that all samples are the pure orthorhombic Ag8SnS6 phase with n-type conductivity. The energy band gaps, carrier concentrations, and mobilities of samples on glass substrates are 131-133 eV, 7.07 x 10(11)-8.52 x 10(12) cm(-3), and 74.9-368 cm(2)V(-1)s(-1), respectively, depending on the [Ag]/[Ag+Sn] molar ratio in samples. The highest photoelectrochemical performances of orthorhombic Ag8SnS6 photoelectrodes in aqueous 0.35 M Na2S + 0.25 M K2SO3 and 0.5 M NaCl solutions are respectively 2.09 and 2.5 mA cm(-2) at an applied voltages of 0.9 and 1.23 V vs. a reversible hydrogen electrode under light irradiation with a light intensity of 100 mW cm(-2) from a 300-W Xe lamp. Crown Copyright (C) 2016 Published by Elsevier B.V. All rights reserved.