A fast and low-cost sol-gel synthesis used to deposit a shell of TiO2 anatase onto an array of vertically aligned ZnO nanowires (NWs) is reported in this paper. The influence of the annealing atmosphere (air or N2) and of the NWs preannealing process, before TiO2 deposition, on both the physicochemical characteristics and photoelectrochemical (PEC) performance of the resulting heterostructure, was studied. The efficient application of the ZnO@TiO2 core-shells for the PEC water-splitting reaction, under simulated solar light illumination (AM 1.5G) solar light illumination in basic media, is here reported for the first time. This application has had a dual function: to enhance the photoactivity of pristine ZnO NWs and to increase the photodegradation stability, because of the protective role of the TiO2 shell. It was found that an air treatment induces a better charge separation and a lower carrier recombination, which in turn are responsible for an improvement in the PEC performance with respect to N2-treated core-shell materials. Finally, a photocurrent of 0.40 mA/cm(2) at 1.23 V versus RHE (2.2 times with respect to the pristine ZnO NWs) was obtained. This achievement can be regarded as a valuable result, considering similar nanostructured electrodes reported in the literature for this application.