Highly porous nano-fibrous poly(L-lactic acid) (PLLA) scaffolds were prepared and incubated in a simulated body fluid which resulted in the in situ formation of partially carbonated bone-like apatite. The macroporous interconnected architecture was created with a three-dimensional mold of thermally-bonded paraffin microspheres. PLLA solution was cast over the paraffin mold and was thermally induced to phase separate to form nano-scale fibers that mimic the fibrous structures of type I collagen. To potentially improve the osteoconductivity of these scaffolds, they were incubated in a buffered simulated body fluid at 37°C for certain periods of time to allow for apatite formation. It was seen that over time, the apatite particles increased in size. In addition, the growth of apatite particles on the nano-fibrous scaffolds was compared with the growth of particles on similar porous PLLA scaffolds with a solid-walled (not nano-fibrous) morphology. It was seen that the initial number of particles per unit area and the overall increase in mass of the scaffolds were significantly higher in the nano-fibrous scaffolds than in the solid-walled scaffolds. These novel scaffolds have well-defined architectures at three different size scales: (i) interconnected spherical pores ∼250–400 m in diameter; (ii) fibrous collagen-like matrix with fibers 50–500 nm in diameter; and (iii) carbonated bone-like apatite particles at the nanometer to micrometer scales; the scaffolds may serve as superior support for bone tissue regeneration.