It has long been pursued to develop polymer microspheres with various special morphologies and structures for better results in applications such as catalysis, drug delivery, and bioscaffolds. However, it remains a challenge to develop a facile method to produce poly(vinyl alcohol) (PVA) microspheres with special morphologies. Herein, a micron-sized marigold-like poly(vinyl alcohol) (C E -PVA TPA ) microsphere was engineered and fabricated by a feasible strategy, that is, emulsification-cross-linking, freeze-drying, and secondary acetal reaction steps. The morphological evolution of microspheres was systematically investigated under different conditions, and the procedure of constructing PVA microspheres with stabilizing marigold-like structures was proposed. More importantly, a specially structured PVA microsphere microreactor synergistically loading palladium metal nanoparticles (C E -PVA TPA @Pd) for the heterogeneous catalyst 4-nitrophenol (4-NP) could be further demonstrated, which indicated high catalytic activity and excellent recyclability. The resultant stabilized fabricating method is promising to provide valuable guidance for the design and fabrication of a high-performance PVA microsphere microreactor.