Maxillofacial bone defects are treated by autografting or filling with synthetic materials in various forms and shapes. Electrospun nanobiomaterials are becoming popular due to their easy placement and handling; combining ideal biomaterials extrapolates better outcomes. We used a novel electrospun cotton-like fiber made from two time-tested bioresorbable materials, β-TCP and PLLA/PGA, to check the feasibility of its application to maxillofacial bone defects through an in vivo rat mandibular bone defect model. Novel β-TCP/PLLA/PGA and pure β-TCP blocks were evaluated for new bone regeneration through assessment of bone volume, inner defect diameter reduction, and bone mineral density. Bioactive/osteoconductivity was checked by scoring the levels of Runt-related transcription factor x, Leptin Receptor, Osteocalcin, and Periostin biomarkers. Bone regeneration in both β-TCP/PLLA/PGA and β-TCP was comparable at initial timepoints. Osteogenic cell accumulation was greater in β-TCP/PLLA/PGA than in β-TCP at initial as well as late phases. Periostin expression was more marked in β-TCP/PLLA/PGA. This study demonstrated comparable results between β-TCP/PLLA/PGA and β-TCP in terms of bone regeneration and bioactivity, even with a small material volume of β-TCP/PLLA/PGA and a decreased percentage of β-TCP. Electrospun β-TCP/PLLA/PGA is an ideal nanobiomaterial for inducing bone regeneration through osteoconductivity and bioresorbability in bony defects of the maxillofacial region.