The architectural design and surface properties of scaffolds are important aspects in tissue engineering. The porous scaffolds accommodate cells and guide their growth, while the surface nature of the scaffolds can directly affect cell attachment, proliferation, and ultimately neo tissue regeneration. In this work, a highly porous poly(L-lactic acid) (PLLA) scaffold with nano-fibrous pore wall architecture has been fabricated by mimicking the structure of natural collagen using a novel thermally induced phase separation method developed in our group. A universally effective surface modification method was developed, and gelatin was successfully grafted onto the surface of nano-fibrous PLLA scaffolds by entrapment procedure. The surface composition, morphology, and properties were examined using ATR-FTIR, XPS and SEM. The surface coverage of gelatin on the PLLA surface was as high as 39.4%. MC3T3-E1 osteoprogenitor cells were cultured for 6 weeks in solid-walled PLLA scaffolds, nano-fibrous PLLA scaffolds, and surface-modified nano-fibrous PLLA scaffolds, respectively. The osteoblasts proliferated in all three types of scaffolds, but the cell numbers were always significantly higher in the surface-modified nano-fibrous scaffolds than in the other two types of scaffolds, and the cell numbers in nano-fibrous scaffolds were higher than that in the solid-walled scaffolds. These results demonstrate that the surface-modified nano-fibrous architecture could serve as a superior scaffold for tissue engineering.