Multi-mode responsive optical materials with versatile application prospects for optical sensing, optoelectrical devices, and information encryption are highly desired. Here we integrate fluorescent carbon dots onto the hollow MnO2 spheres, and modulate the interaction between them to achieve a water-stimulated responsive system with dual-mode dynamic signals in both fluorescence and structural color. The composite film shows a structural color shifting from blue to green as well as displays a fluorescence “on” in the presence of trace water, with both changes capable of being reversibly switched up to 10 times. The amide bond between the two components enables the controllable dispersion and aggregation of the carbon dots which is essential to the reversibility. Fabrication of several security labels with separate information in structural color and fluorescence channels demonstrates the application potential of the composite. This work provides a concise route to develop new multi-mode responsive optical materials for applications in anti-counterfeiting, sensing, and coding.