This work reports the synthesis of Au@Cu2O core@shell nanocrystals with controllable shell thicknesses and demonstrates their use as the dual-functional catalyst that can continuously operate under illumination and darkness conditions for efficient E. con inactivation. On account of the peroxidase mimics of the Au core and Fenton reactivity of the Cu2O shell, the Au@Cu2O nanocrystals exhibit intrinsic peroxidase-like property with the reaction kinetics in accordance with the typical Michaelis-Menten mechanism. On the other hand, time resolved photoluminescence spectra suggest the prevalence of pronounced charge separation for Au@Cu2O nanocrystals, an important advantage that is favourable for photocatalysis. By combining the photocatalytic capability with the peroxidase mimics features, Au@Cu2O nanocrystals can perform practical photocatalytic decomposition of E. coil under visible light illumination but still show vital activity towards E. coil inactivation after light illumination was turned off. The current study delivers a new catalyst configuration by exploiting the multiple functionalities of nanosized Au and Cu2O for advanced environmental and energy conversion applications.