Poly-L-lactide (PLLA)/natural hydroxyapatite (n-HA) composite scaffolds with different morphology and porosity were prepared using thermally induced phase separation (TIPS) 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 double-stranded deoxyribonucleic acid (ds-DNA) adsorption behavior was investigating with the aim of their applications in gene therapy. The propensity of the scaffolds and n-HA particles to adsorb ds-DNA was assessed by batch experiments at pH 4. The aggregated size of the ds-DNA molecules and agglomeration after adsorption were characterized by dynamic light scattering (DLS) and Fourier transform infrared (FTIR) spectroscopic imaging. The adsorption data were fitted into the Freundlich equation and the adsorption parameters were assessed. Although the adsorption capacity of the scaffolds was lower as compared to n-HA particles, it was sufficient for ds-DNA adsorption. The in vitro cell culture test was conducted on the scaffolds with human mesenchymal stem cells (hMSCs). The cells on PLLA/n-HA/ds-DNA scaffold showed more significant increases than neat PLLA and PLLA/n-HA scaffolds. (C) 2014 Elsevier Ltd. All rights reserved.