In order to prepare nano-hydroxyapatite/poly(lactide) (n-HA/PLA) composite with good interfacial interaction, some groups which could bind with Ca ions in HA crystals need to be introduced onto PLA surface. Poly(α-methacrylic acid) (PMAA) was grafted on the PLA surfaces via photooxidization and subsequent UV induced polymerization. Suspension of PMAA-PLA microparticles with an average size as 133.1nm was prepared with solvent evaporation technique. Then utilizing the action of template manipulating of PMAA-PLA microparticles, n-HA/PLA composite were synthesized. Zeta potentials measurement and SEM indicated that there were good interfacial interactions between two phases of n-HA/PLA composite. The results of cell viability confirmed that n-HA/PLA composite possessed good cytocompatibility, so the n-HA/PLA composite scaffold obtained by electrospun technology might be used as bone tissue engineering scaffold.