Poly(ethylene-co-vinylacetate) (EVA) microspheres were prepared by a thermally induced phase separation. Poly(vinyl Alcohol) (EVAL) microsphere with Core-Shell Structure were synthesized by a saponification on sheath of EVA microspheres. The size of EVA core/EVAL shell microsphere was decreased from 4.09㎛ to 2.55㎛ by partial saponification of NaOH/Na2SO4/methanol(2 : 1 : 1 by weight) at 60℃ for 4h to produce a saponified surface layer of about 60% of original radius. In this process, the surface layer of EVAL microsphere was dissolved partially and morphology of surface was not showed. Add-on of cotton and silk printed with EVA core/EVAL shell microsphere was increased and that of printed PET was decreased. In case of EVA core/EVAL shell microsphere, Hand of cotton and silk printed was flexible and fullness.