Bone tissue engineering (BTE) has emerged as an option for creating new bone substitutes for application in bone tissue defects. The materials used for making the scaffolds have been based on FDA-approved synthetic polymers such as poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) for their biodegradable, biocompatible, and mechanical properties. Moreover, one biopolymer, gelatin (Gt), has been used as a functional coating for its biological properties. In BTE, a combination of techniques has emerged for developing different microarchitectures that could imitate the extracellular matrix (ECM) of native bone. In this work, we try to combine electrospinning and 3D printing to create a bone scaffold with improved topological properties. We produce coaxial nanofibers (CNF) of PCL/Gt and PLA/Gt for coating circular porous 3D printing scaffolds using electrospinning. The characterization by SEM showed the fibrillar structures with interconnected pores with random alignment, and TEM indicated the formation of the core–shell structure. FTIR and thermal analysis showed the characteristic signals of each component and no apparent effect on the decomposition stages of each material, respectively. The biological characterization of the 3D scaffold coating showed improved adhesion in 24 h and good biocompatibility and bioactivity of human fetal osteoblasts over the 21 days of culture. In conclusion, our results showed that CNF-coated scaffolds achieve improved topological properties by functionalizing Gt-based coaxial electrospun nanofibers with potential use in BTE. The authors want to thank the financial support by CONAHCYT for the scholarship granted for the doctoral study of CETS with CVU 1009583 and the financial support given by the DGAPA-UNAM-PAPIIT IN202924, IN106624, and PAIP 5000-9222 projects.