The development of optical materials with room temperature phosphorescence (RTP) and white light emission (WLEDs) is highly desirable and remains a challenging task. Herein, a porous metal–organic framework PCN-921 with a high quantum yield (Φ_F = 93.6%) was achieved. To make full use of the advantages of the high porosity of PCN-921, we hierarchically encapsulated different guest molecules coronene and rhodamine B (RhB) into the framework. Unsurprisingly, the hybrid material coronene@PCN-921 was obtained after in situ encapsulation of the guest coronene into the framework, and it exhibits obvious RTP behavior with a long phosphorescence lifetime of 62.5 ns. Subsequently, second guest RhB molecules were introduced after soaking in RhB solution and the material RhB@coronene@PCN-921 was achieved. Interestingly, it exhibits white light emission with the CIE coordinates of (0.29, 0.34), and can be used as a high performance WLED lamp. This is the first work on dual-functional hybrid dyes@MOFs with hierarchical guest encapsulation for RTP and white light emission, which suggests the potential applications of MOFs in multifunctional optical devices.