A novel 3D bioprinting of porous scaffold was developed by using highly concentrated alginate/polyvinyl alcohol (PVA) as building block for tissue engineering. PVA sols were partly diffused from the printed scaffolds during incubation in CaCl₂ solution, creating plenty of micropores in scaffolds. The properties of the as-prepared scaffolds such as porosity, water adsorption and mechanical properties, can be tailored by adjusting the mass ratio of alginate/PVA. Meanwhile, bovine serum albumin and bone morphogenetic protein 2 were successfully co-printed into scaffolds, and their release behavior depended on the micropores.