Abstract Long‐lived room temperature phosphorescence (RTP) materials have many potential applications in areas such as luminescent lighting, biological imaging, and information security owing to their unique optical properties. However, traditional RTP materials are challenged by the fact that their phosphorescence can be easily quenched by dissolved oxygen and solvent‐assisted relaxation, making it difficult for them to emit phosphorescence in aqueous solutions, particularly in extreme pH environments. In this study, a multicolor RTP carbon dot‐based composite material (u‐CDs) is developed with urea and 3‐aminophenylboronic acid as raw materials. This material exhibits ultra‐long phosphorescence emission lifetime and high pH stability by constructing a rigid hydrogen bond network structure in an aqueous environment. The u‐CDs have an optimal emission of 448 nm, a quantum yield of 21.6%, a phosphorescence lifetime of 2.35 s, and an afterglow time of more than 50 s. With such unique properties, u‐CDs have great potential for applications in anti‐counterfeiting, information encryption, and 3D printing.