A tetragonal polyvinyl alcohol (PVA) scaffold with 3D orthogonal periodic porous architecture was fabricated via selective laser sintering (SLS) technology. The scaffold was fabricated under the laser power of 8 W, scan speed of 600 mm min(-1), laser spot diameter of 0.8 mm and layer thickness of 0.15 mm. The microstructure analysis showed that the degree of crystallization decreased while the PVA powder melts gradually and fuses together completely with laser power increasing. Thermal decomposition would occur if the laser power was further higher (16 W or higher in the case). The porous architecture was controllable and totally interconnected. The porosity of the fabricated scaffolds was measured to be 67.9 ± 2.7% which satisfies the requirement of micro-pores of the bone scaffolds. Its bioactivity and biocompatibility were also evaluated in vitro as tissue engineering (TE) scaffolds. In vitro adhesion assay showed that the amount of pores increased while the scaffold remains stable and intact after immersion in simulated body fluid for seven days. Moreover, the number of MG-63 cells and the bridge between cells increased with increasing time in cell culture. The present work demonstrates that PVA scaffolds with well-defined porous architectures via SLS technology were designed and fabricated for bone TE.