Polymer and ceramic composite scaffolds play a crucial role in bone tissue engineering. In an attempt to mimic the architecture of natural extracellular matrix (ECM), poly(l-lactic acid)/β-tricalcium phosphate (PLLA/β-TCP) nanocomposite scaffolds with a hierarchical pore structure were fabricated by combining thermal induced phase separation and salt leaching techniques. The nanocomposite scaffold consisted of a nanofibrous PLLA matrix with a highly interconnected, high porosity (>93%) hierarchical pore structure with pore diameters ranging from 500nm to 300μm and a homogeneously distributed β-TCP nanoparticle phase. The nanofibrous PLLA matrix had a fiber diameter of 70–300nm. The nanocomposite scaffolds possess three levels of hierarchical structure: (1) porosity; (2) nanofibrous PLLA struts comprising the pore walls; and (3) β-TCP nanoparticle phase. The β-TCP nanoparticle phase improved the mechanical properties and bioactivity of the PLLA matrix. The nanocomposite scaffolds supported MG-63 osteoblast proliferation, penetration, and ECM deposition, indicating the potential of PLLA/β-TCP nanocomposite scaffolds with hierarchical porosity for bone tissue engineering applications.