Biodegradable polymeric nanofibrosus meshes have emerged as a choice of scaffolds for cells to attach and grow as they mimic closely the nanoscale morphology of native extracellular proteins and promote cell-growth. Electrospun fibrous nanocomposite scaffolds of biodegradable synthetic polymer polycaprolactone (PCL) with surface modified carbon nanofibers (mCNFs) were successfully fabricated using the electrostatic co-spinning process. Structural and morphological properties of the nanofibrous composite scaffolds were characterized using, SEM, TEM, TGA and XRD. Microscopic analyses showed bead-free nanofibrous morphology with the presence of mCNFs in the electrospun scaffolds. The overall scaffolds' crystallinity and degree of orientation were assessed using XRD. The mechanical properties of the electrospun scaffolds as evaluated with tensile test, showed a marked increase in strength and stiffness with nanofiber alignment and with addition of mCNFs (0.1 and 0.5 wt %). Human mesenchymal stem cells (hMSCs) cultured onto PCL/mCNFs scaffold showed successful attachment and spreading of the cells. © 2012 Bentham Science Publishers.