Shape-controlled block copolymer (BCP) particles that respond to light stimulus have drawn great attention due to their promising applications in smart materials, yet polymeric particles with light-triggered controllable sequential shape transformation (SST) are still rarely reported. By confined co-assembly of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) and azo-containing light-responsive additives within emulsions, herein, we fabricated BCP particles with light-controlled SST behavior. Attributed to the quaternization of P2VP chains with bromoalkyl additives and the trans-cis isomerization of an azo group under UV light, the interfacial interactions between the BCPs and the surrounding aqueous phase are significantly varied; therefore, the particles exhibit three distinct phases in sequence: (1) elongation of ellipsoidal particles with increasing domain spacing; (2) shape transformation of elongated ellipsoidal particles into accordion-like particles; and (3) disassembly of polymer particles into small spheres. In addition, these particles with SST behavior can be used in light-controlled drug release at a high spatial-temporal resolution, demonstrating their potential in clinical settings and biomedicine.