This study has demonstrated a facile but efficient synthesis method to prepare vanadium oxide@titanium oxide (V2O5@TiO2) core–shell nanostructures using a water bath at mild temperatures (≤100 °C). This method shows a few unique features, including a short reaction time for fabricating core–shell nanostructures, no requirement of high temperature calcination (>500 °C) for TiO2 crystallization, easily tunable TiO2 shell thickness, high yield, and good reproducibility. With characterization using several advanced techniques (TEM, BET, XRD, XPS and UV-vis spectroscopy), the as-prepared V2O5@TiO2 nanocomposites were found to exhibit a large surface area, and a good stability. The experimental results show that the V2O5@TiO2 core–shell composites show a superior sunlight photocatalytic activity compared to the pure TiO2 nanoparticles for the degradation of organic dyes (e.g., methylene blue), probably because of the matched energy bands between V2O5 and TiO2. These findings may bring new insights into the designing of TiO2-based core–shell and other nanocomposites with enhanced photocatalytic efficiencies for environmental remediation.