The regeneration of the lost tissues or organs due to accidents or diseases is major concern in modern health care. With tissue engineering we can create biological substitutes to repair or replace the failing organs or tissues. PLLA scaffolds are becoming popular these days with its biodegradable and biocompatible nature. Hydroxyapatites have been widely used as gene or drug vehicles because of their good adsorption, high transfection efficiency and nontoxicity. In this study, we prepared PLLA/HA composite scaffolds having open pore structure and investigated the structure development of the composite scaffolds in different feed concentration of the PLLA/HA. PLLA/HA composite scaffolds with different morphology and porosity were prepared using thermally induced phase separation　technique. The morphological features of the scaffolds were observed by field emission scanning electron microscope (FE-SEM). The solvent concentration had much effect on the porosity and pore morphology. The DNA adsorption behavior was investigating with the aim of their applications in gene therapy. In vitro cell culture was used to analyze the biocompatibility of the PLLA/HA/DNA scaffolds. Dynamic Light Scattering (DLS) and zeta potential measurements characterized the double-stranded deoxyribonucleic acid (ds-DNA). The propensity of the scaffolds and HA particles to adsorb ds-DNA were assessed by batch experiments at pH 4. The adsorption data were fitted into the Freundlich equation and the adsorption parameters were assessed. Although the adsorption capacity of the scaffolds lower as compared to just HA particles, it was sufficient for DNA adsorption. The in vitro cell culture test was conducted on PLLA/HA/DNA scaffolds with human mesenchymal stem cells. The cells on PLLA/HA/DNA scaffolds showed more significant increases than neat PLLA and PLLA/HA scaffolds. These results suggested that the newly developed PLLA/HA modified by DNA might be a superior material for tissue engineering.