Biodegradable polymers have a mean role to mimic native tissues and allow cells to penetrate, grow, and proliferate with their advanced features in tissue engineering applications. The physiological, chemical, mechanical, and biological qualities of the surfaces, which are presented from biodegradable polymers, affect the final properties of the scaffolds. In this study, it is aimed to produce fibrous webs by electrospinning method for tissue engineering applications using two different biopolymers, polylactic acid (PLA) and polycaprolactone (PCL). These polymers are used either alone or in a blended form (PLA/PCL, 1/1 wt.). Within the scope of the study, polymer concentrations (6, 8 and 10%) and solvent types (used for chloroform/ethanol/acetic acid mixture, PCL and PLA/PCL mixtures, and chloroform/acetone, PLA) vary as solution parameters. Fibrous webs are investigated in terms of morphological, chemical, and thermal characteristics. Results show continuous fibers are examined for 8 or 10% polymer concentrations with an average fiber diameter of 1.3–2.7 μm and pore area of 4–9 μm2. No fiber formation is observed in sample groups with a polymer concentration of 6% and beaded structures are formed. Water contact angle analysis proves the hydrophobic properties of PLA and PCL, whereas Fourier‐transform infrared results show there is no solution residue on the surfaces, so there is no toxic effect. Also, in differential scanning calorimetry analysis, the characteristic crystallization peaks of the polymers are recognized, and when the polymers are in a blend, it beholds that they have effects on each other's crystallization.