To determine the optimal ratio of nano-hydroxyapatite (n-HA) to polylactic acid (PLLA) in the novel three-dimensional porous PLLA/n-HA composite scaffolds, low-temperature rapid prototyping technology was employed to fabricate the composite materials with different n-HA contents. Mechanical properties and degradation behaviors of the composites were examined, and the scaffold microstructure and n-HA dispersion were observed by scanning electron microscope (SEM). Mechanical tests demonstrated that the tensile strength of the composite material gradually decreased with an increase in n-HA content. When the n-HA content reached 20 wt%, the bending strength of the composite material peaked at 138.5 MPa. SEM images demonstrated that the optimal content of n-HA was 20 wt% as the largest interconnected pore size that can be seen, with a porosity as high as 80%. In vitro degradation experiments demonstrated that the pH value of the material containing solution gradually decreased in a time-dependent manner, with a simultaneous weakening of the mechanical properties. In vitro study using rat osteoblast cells showed that the composite scaffolds were biocompatible; the 20 wt% n-HA scaffold offered particular improvement to rat osteoblast cell adhesion and proliferation compared to other compositions. It was therefore concluded that 20 wt% n-HA is the optimal nano-hydroxyapatite (n-HA) to polylactic acid (PLLA) ratio, with promise for bone tissue engineering.