Octacalcium phosphate (OCP) was synthesized yielding a combination of OCP and hydroxyapatite (HA) with a ratio of 90:10 (OCP/HA). A method was developed to functionalize the surface of the apatite using lauroyl chloride to improve the dispersion of the mineral phase in a poly(L-lactide) (PLLA) polymeric matrix. Infrared spectra and thermal gravimetric analysis confirmed the presence of laurate on the surface of calcium phosphate (CaP) particles. Neat HA particles were also functionalized with lauryl chloride for comparative purposes. PLLA/OCP/HA-laurate (PLLA/OCP/HA-L) and PLLA/HA-laurate (PLLA/HA-L) composites were fabricated by electrospinning method. The presence of the functional groups resulted in significant improvement of the dispersion of OCP/HA and HA particles into the polymeric matrix, allowing inclusion of up to 40% of mineral phase. Electrospun fibrous biocomposites of PLLA/CaP containing up to 40% in mineral phase were obtained without compromising their mechanical properties. Measurements of mass loss and calcium release in vitro showed that OCP/HA is more soluble than HA. The bioactivity of the composites was investigated by simulated body fluid test (SBF). Although both PLLA/OCP/HA-L and PLLA/HA-L fibers can form CaP crystals on their surface after exposition in SBF, the results demonstrate a significant enhancement in mineralization when OCP/HA is the mineral phase in the composite instead neat HA. Furthermore, the obtained PLLA/OCP/HA-L electrospun fibers favored the proliferation and differentiation of stem cells from human exfoliated deciduous teeth and mouse calvaria-derived preosteoblastic cells into mineralized osteoblasts. This new material is proposed as fast degrading CaP biocomposite for bone and teeth applications.