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AgGaSe2 films were brush electrodeposited on tin oxide coated glass substrates at different substrate temperatures. The films were single phase with chalcopyrite structure. Optical absorption measurements indicated a band gap in the range of 1.74 eV to 1.94 eV with decrease of substrate temperature. AgGaSe2 films were deposited on tin oxide coated conducting glass substrates at different substrate temperature in the range of 30–80°C at a deposition current density of 5.0 mA cm-2. Thickness of the films varied in the range of 700 – 1200 nm with increase of substrate temperature. Photoelectrochemical solar cells were fabricated using the films. The photoelectrodes post heat treated at 550°C exhibited a Voc of 0.475V, Jsc of 4.30 mA cm-2 and a conversion efficiency of 1.43 %. After photoetching, the conversion efficiency increased to 3.0 %.