The development of particles that possess different properties has been a long‐thought goal for producing multifunctional materials owing to their combination of performance. Herein, aggregation‐induced emission (AIE) gemini surfactant‐assisted preparation of shape‐controlled fluorescent hollow silica nanoparticles (AIE‐SNs) is performed directly in water through a one‐pot method. The incorporated AIE gemini surfactant (C16‐TPE‐C16) not only provides a fluorophore for the AIE‐SNs but also participates in the structure‐directing process with cetyltrimethylammonium bromide (CTAB) to regulate their construction. By properly tuning the molar ratio of CTAB and C16‐TPE‐C16, AIE‐SNs with different morphologies and fluorescence properties can be produced. Their mesoporous silica nanoparticle (AIE‐MSN) derivatives can also be fabricated by subsequent extraction owing to the inherent structural differences between CTAB and C16‐TPE‐C16. Importantly, fluorescent hollow mesoporous silica nanorods and nanospheres with ordered channels, thin shell thicknesses (~ 13 and ~ 7 nm), high accessible surface areas (599.2 and 573.9 m2 g–1), and uniform pore sizes ~ 2.8 nm) can be facilely prepared at CTAB/C16‐TPE‐C16 molar ratios of 30:1 and 15:1, respectively. This facile and straightforward method for creating tunable hollow AIE‐MSNs may open viable opportunities and inspire the preparation of particles with multiple properties.
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