A method of sequential spraying of polyvinyl alcohol with carbon quantum dots (PVA@CDs) aqueous suspension and SiO2 aqueous suspension is proposed to rapidly prepare multicolor dual-mode anti-counterfeiting labels. With the optimization of the concentration (15%) of colloidal microspheres in the SiO2 aqueous suspension as well as the spraying process parameters (spray distance of 10 cm, spray duration of 3 s, and assembly temperature of 20 °C), different-sized SiO2 microspheres (168 nm, 228 nm, and 263 nm) were utilized to rapidly assemble red, green, and blue photonic crystals. Furthermore, the tunable fluorescence emission of carbon quantum dots endows the labels with yellow, green, and blue fluorescence. The constructed dual-mode labeling was used to develop an anti-counterfeiting code with dual-channel information storage capabilities and also to create dual-mode multicolor anti-counterfeiting labels on various packaging substrates. This work provides a novel solution for anti-counterfeiting packaging and information storage.