In this communication, we developed the first well-controlled Z-RAFT (RAFT = reversible addition–fragmentation chain transfer) mediated polymerization-induced self-assembly (PISA) formulation based on photoinitiated RAFT dispersion polymerization of tert-butyl acrylate (tBA) in ethanol/water (60/40, w/w) at room temperature using a Z-type macromolecular chain transfer agent (macro-CTA). Polymerizations proceeded rapidly via the exposure of visible-light irradiation (405 nm, 0.45 mW/cm²) with high monomer conversion (>95%) being achieved within 1 h. A variety of polymer nano-objects (spheres, worms, and vesicles) with narrow molar mass distributions were prepared by this Z-RAFT mediated PISA formulation. Silver nanoparticles were loaded with the vesicles via in situ reduction, which can be used as a catalyst for the reduction of methylene blue (MB) in the presence of NaBH₄. Finally, gel permeation chromatography (GPC) analysis demonstrated that the corona block and the core-forming block could be cleaved by treating with excess initiator. This novel PISA formulation will greatly expand the scope of PISA and provide more mechanistic insights into the PISA research.