The present invention relates to a process for forming a porous poly(vinyl alcohol) (PVA) scaffold using a pore-forming agent, and more particularly, to a process for forming a porous PVA scaffold using a pore-forming agent, comprising: mixing PVA with the pore-forming agent to form micropores in the PVA scaffold and using an easily decomposable pore-forming agent after the formation of the pores to improve convenience and reduce the processing time in manufacturing the porous PVA scaffold as well as to enable a pore size and porosity to be selected. A process for forming a porous PVA scaffold using a pore-forming agent according to the present invention includes heating to melt the PVA, cooling the melted PVA and mixing the PVA with a heat-decomposable pore-forming agent, repeating the freezing/thawing of the mixed PVA to cure the PVA mixture, and stirring the cured PVA mixture with a hydrochloric acid solution at a high temperature of 65°C or more to produce foam.