This paper presents a two-step approach for electrospinning of hydroxyapatite/chitosan (HAp/CTS) nanocomposite, which was firstly prepared by an in situ co-precipitation method. Continuous HAp/CTS nanofibers with diameters of 214 ± 25 nm were produced successfully with the aid of an ultrahigh molecular weight poly(ethylene oxide) (UHMWPEO). The HAp nanoparticles with aggregations to some extent were incorporated along the electrospun CTS-based nanofibers. And their crystallite structure can be preserved to some extent although an acidic solvent system was used. Current nanocomposite nanofibers of HAp/CTS may be of potential interest for bone repair and regeneration application.