Chemical treatment of polycaprolactone was carried out to bioactivite the biodegradable polymer for bone tissue engineering application. The results show that surface modifications are necessary to introduce functional groups such as carboxylic groups for the effective induction of apatite nucleation, prior to SBF treatment. The functional groups, acting as anchors between the polymer and the apatite nuclei, dictate the duration of the induction period need for apatite nucleation. After the surface treatment with sodium hydroxide solution, the apatite nuclei will form and grow spontaneously into a dense and uniform layer of apatite, by taking up Ca2+ and PO4 2- ions that are present in the SBF, as SBF is supersaturated with respect to apatite. Similar surface treatment was applied to electrospun PCL nanofibres. Biomimetic apatite/PCL nanofibres were formed which can potentially be used as bone tissue engineering scaffolds.