Hydrogen(H2) production using solar power is being researched on all scales. Apart fromlarge scale installations, a photoelectrochemical (PEC) electrolyzer (a small scale set-up) isalso a promising way of converting light to H2 for smaller applications wherephotoelectrodes produce H2 from electrolysis. Initially, for this study, variousphotoelectrodes, tungsten-tri-oxide (WO3) and copper gallium selenide (CuGaSe2) wereanalysed one being photoanode and the other being photocathode respectively. They arecompared for their electrochemical characterizations like current density, stability and gasevolution using techniques like linear sweep voltammetry (LSV), chronoamperometry (CA)and chronopotentiomery (CP). Apart from the above mentioned titanium-di-oxide (TiO2)and copper chromium oxide (CuCrO2) were also investigated.At a later stage gas evolution and gas chromatography (GC) was first tested using Platinumelectrodes as a preliminary study. CuGaSe2 being the most photoactive material incomparison to other photoelectrodes researched upon, this material was further chosen tobe investigated on a larger active area of 5×5 cm2from 0.5 cm2. However, this was notpossible as gas evolution was not observed using the large sample probably due to impropersample preparation. Hence, an electrode with an active area of 3.5 cm2 was chosen in acombination of photovoltaic- photoelectrochemical (PV-PEC) set-up where a 3-cell PVmodule was connected to the PEC cell and illuminated. This resulted in a working model.The PV-PEC set-up with CuGaSe2 having an active area of 3.5 cm2 was observed to have aconsiderable amount of gas evolution. The evolved gas was collected in small samples andfurther analysed for individual H2 and Oxygen (O2 ) gas concentrations by injecting it into agas chromatograph. As a result, the volume of evolved H2 gas was thrice lower than thetheoretically calculated values indicating a Faradaic efficiency of 34.8 %, where the ideal caseis 100 %. Furthermore, the resulting solar-to-hydrogen (STH) efficiency also resulted as 0.03%.With the selected materials an STH close to 1 % was expected. However, this was very farto achieve. Proper sample preparation would have yielded higher STH values with CuGaSe2material.