This work has focused on the development of electrospun TiO2 fiber composite photoelectrodes for hydrogen production by water splitting. For comparison, similar photoelectrodes were also developed using commercial TiO2 (Aeroxide P25) nanoparticles (NPs). Dispersions of either fibers or P25 NPs were used to make homogenous TiO2 films on fluorine-doped SnO2 (FTO) glass substrates by a doctor blade (DB) technique. Scanning electron microscopy (SEM) analysis revealed a much lower packing density of the DB fibers, with respect to DB-P25 TiO2 NPs; this was also directly reflected by the higher photocurrent measured for the NPs when irradiating the photoelectrodes at a light intensity of 1.5AM (1 sun, 1000 W/m(2)). For a better comparison of fibers vs. NPs, composite photoelectrodes by dip-coating (onto FTO) TiO2 sol-gel (SG) matrixes containing an equal amount (5 or 20 wt %) of either fibers or P25 NPs were also investigated. It emerged that the photoactivity of the fibers was significantly higher. For composites containing 5 wt % TiO2 fibers, a photocurrent of 0.5 mA/cm(2) (at 0.23 V vs Ag/AgCl) was measured, whereas 5 wt % P25 NPs only provided 0.2 mA/cm(2). When increasing to 20 wt % fibers or NPs, the photocurrent decreased, because of the formation of microcracks in the photoelectrodes, because of the shrinkage of the sol-gel. The high photoactivity of the fiber-based electrodes could be confirmed by incident photon to current efficiency (IPCE) measurements. Remarkably, the IPCE of composites containing 5 wt % fibers was between 35% and 40% in the region of 380-320 nm, and when accounting for transmission/reflection losses, the absorbed photon to current efficiency (APCE) was consistently over 60% between 380 nm and 320 nm. The superior photoactivity is attributed to the enhanced electron transport in the electrospun fibers, with respect to P25 NPs. According to this study, it is clear that the electronic connectivity ensured by the sol-gel also contributes positively to the enhanced photocurrent.