Recent advances in cell transplantation technologies have shown that polymeric fibrous tissue-engineered scaffolds provide a suitable physical environment, including the structural support, for cell delivery and effectively mimic the transplanted cells’ extracellular matrix. Our study investigates the structure, composition and properties of three most commonly used polyester-based biopolymer materials blended with poly(ε-caprolactone) (PCL) at 2:1 (wt.%) ratio, namely, poly(glycerol sebacate) (PGS)/PCL, polylactic-co-glycolic acid (PLGA)/PCL, poly-l-lactide (PLLA)/PCL and pure PCL as carrier vehicles for retinal progenitor cell (RPC) attachment and RPC proliferation. The physicochemical properties of PGS/PCL, PLLA/PCL, PLGA/PCL and pure PCL fibrous scaffolds, fabricated under the identical electrospinning conditions, were analysed employing scanning electron microscopy, contact angle analysis, Raman spectroscopy, electrical and ionic conductivity measurements, and supplemented by an in-vitro RPC adhesion and proliferation studies. Our findings have shown that PGS/PCL scaffolds promote RPC attachment and RPC proliferation more favourably compared to other polymeric blends and pure PCL, owing to a combination of advantageous surface and bulk properties, overall demonstrating a potential for PGS/PCL blend to become a suitable vehicle for RPC delivery in a possible future clinical therapy for the treatment of retinal degenerative disorders.