Copper oxides are promising photocathode materials for solar hydrogen production due to their narrow optical band gap energy allowing broad visible light absorption. However, they suffer from severe photocorrosion upon illumination, mainly due to copper reduction. Nanostructuring has been proven to enhance the photoresponse of CuO photocathodes; however, there is a lack of precise structural control on the nanoscale upon sol–gel synthesis and calcination for achieving optically transparent CuO thin film photoabsorbers. In this study, nanoporous and nanocrystalline CuO networks were prepared by a soft-templating and dip-coating method utilizing poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic® F-127) as a structure-directing agent, resulting for the first-time in uniformly structured, crack-free, and optically transparent CuO thin films. The photoelectrochemical properties of the nanoporous CuO frameworks were investigated as a function of the calcination temperature and film thickness, revealing important information about the photocurrent, photostability, and photovoltage. Based on surface photovoltage spectroscopy (SPV), the films are p-type and generate up to 60 mV photovoltage at 2.0 eV (0.050 mW cm⁻²) irradiation for the film annealed at 750 °C. For these high annealing temperatures, the nanocrystalline domains in the thin film structure are more developed, resulting in improved electronic quality. In aqueous electrolytes with or without methyl viologen (as a fast electron acceptor), CuO films show cathodic photocurrents of up to −2.4 mA cm⁻² at 0.32 V vs. RHE (air mass (AM) 1.5). However, the photocurrents were found to be entirely due to photocorrosion of the films and decay to near zero over the course of 20 min under AM 1.5 illumination. These fundamental results on the structural and morphological development upon calcination provide a direction and show the necessity for further (surface) treatment of sol–gel derived CuO photocathodes for photoelectrochemical applications. The study demonstrates how to control the size of nanopores starting from mesopore formation at 400 °C to the evolution of macroporous frameworks at 750 °C.