In advanced disease or accidental injuries, the replacement of small diameter blood vessel is inevitable and tissue engineering has created a hope to replace the vascular auto grafts with synthetic grafts in unavoidable situations. However, the contemporary constraints of available small-diameter artificial vascular grafts (SDAVG) like, requirements for anticoagulant therapy, intimal hyperplasia, and aneurysm formation limit their performance. Numerous approaches and biomaterials have been attempted to address this issue with limited success. In a step towards the development of SDAVG we explore Polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) a fluoropolymer with reduced inflammation, increased re-endothelialisation and thrombo-resistance properties based scaffold. Fibrous scaffolds of PVDF-HFP were developed using electrospinning (to provide porous mat with resemblance to native extracellular matrix), and their performance for bone marrow derived endothelial cell (BMEC) adhesion and proliferation were compared with solid cast surfaces. The effect of scaffold surface physical properties and chemical factor such as pre-adsorbed fibrinogen (PAF), on endothelial cell adhesion and proliferation was also examined. BMEC morphology, proliferation, viability and fibrinogen quantification were analysed by scanning electron microscope, WST-1 proliferation assay and X-ray photoelectron spectroscopy (XPS). Pristine solid and TCP surfaces have shown good adhesion and proliferation (217200 ±10700 cells/cm2) with moderate spreading of BMEC due to their hydrophobic nature. While the fibrous electrospun scaffolds, which are near super hydrophobic have shown less and slow BMEC adhesion and proliferation (131200±7254cells/cm2). There was no difference of adhesion and proliferation observed on pristine and pre-adsorbed fibrinogen solid surfaces; but on fibrous scaffolds there was good adhesion and complete proliferation (253410±13432 cells/cm2) of BMEC on PAF surfaces with good spreading. Therefore, physical and chemical properties of a scaffold can induce a great influence on the performance of the scaffold. The large surface area of fibrous scaffold can provide good adsorption of biomolecules and subsequent proliferation of endothelial cells.