A new synthetic approach has been developed to prepare silver@titanium dioxide (Ag@TiO2) core-shell nanostructures with controllable size, shape, crystal phase and function at ambient conditions (e.g. in water, ≤100 ° C). This approach shows a few unique features, including short reaction time (a few minutes) for forming core-shell nanostructures, no requirement of high temperature calcinations for generating TiO2 (e.g. at ~100 ° C in our case), tunable TiO2 shell thickness, high yield and good reproducibility. The experimental results show that the Ag@TiO2 core-shell nanostructures exhibit excellent photocatalytic activity compared to the commercial TiO2 (P25) and Ag-doped TiO2 nanocomposite in the degradation of organic dye molecules (e.g. methyl orange) with ultraviolet (UV) irradiation. This could be attributed to the large surface area of TiO2 nanoparticles for maximum harvesting of UV light, mixed anatase and rutile crystalline phases in the TiO2 shell and the effective charge separation between Ag and TiO2 that can reduce the possible recombination of electron-hole (e(-)-h(+)) pairs within TiO2 generated under UV radiation. To further understand the charge separation situation within Ag-TiO2 composites, theoretical simulation (e.g. density functional theory, DFT) was employed in this study. The DFT simulation results indicate that for the Ag@TiO2 core-shell nanostructures, photo-generated electrons transfer readily from the external TiO2 layer to the internal Ag layer with heavy accumulation compared to those doping Ag on TiO2 surfaces, which may reduce the recombination of e(-)-h(+) pairs and thus enhance the photocatalytic efficiency. The findings may open a new strategy to synthesize TiO2-based photocatalysts with highly enhanced efficiency for environmental remediation applications.