The thermo-responsive vesicles of poly[N-(4-vinylbenzyl)-N,N-diethylamine]-b-polystyrene (PVEA-b-PS) and the nanospheres of poly(acrylic acid)-b-polystyrene (PAA-b-PS) were prepared and the blending of the PVEA-b-PS vesicles and the PAA-b-PS nanospheres to form vesicle/nanospheres complexes and the revisable disassembly of the vesicle/nanospheres complexes were investigated. Through the in situ synthesis strategy of the macro-RAFT agent mediated dispersion polymerization, well-defined PVEA-b-PS vesicles and PAA-b-PS nanospheres were prepared. Due to the hydrogen bonding between the amino groups embedded in the PVEA-b-PS vesicles and the carboxylic acid groups in the PAA-b-PS nanospheres, the vesicle/nanospheres complexes, in which the small-sized PAA-b-PS nanospheres are adhered onto the outer surface of the large-sized PVEA-b-PS vesicles, were formed, when the PVEA-b-PS vesicles and the PAA-b-PS nanospheres were blended. It was found that the morphology of the vesicle/nanospheres complexes dispersed in methanol was tuned with the molar ratio of the fed PAA-b-PS nanospheres to the PVEA-b-PS vesicles. Ascribed to the thermo-response of the PVEA block, which shows the soluble-to-insoluble phase transition in methanol at the phase transition temperature (PTT) of 44 °C, the vesicle/nanospheres complexes reversibly converted into individual PAA-b-PS nanospheres and PVEA-b-PS vesicles when temperature increased above PTT.