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In the current study, a mixture of formic acid (FA), acetic acid (AA), and acetone was used, for the first time, as a ternary solvent system to dissolve poly(ɛ-caprolactone) (PCL). In addition, as a biomaterial reinforcement, various amounts of cellulose microfibrils (CMF) (1.5, 3, and 5 wt.%), extracted from rice husk, were added to PCL solution, and subsequently the prepared suspensions were individually electrospun. Adding acetone to FA/AA solvent system led to fabrication of uniform electrospun nanofibers with the average diameter of 178 ± 38 nm. Upon CMF incorporation, the mean electrospun fiber diameter was increased to 320 ± 132 nm at 5 wt.% CMF mostly due to the solution viscosity rise. In addition, scanning electron microscopy (SEM) confirmed wider diameter distribution in the presence of CMF. The electrospun fibers were also analyzed via wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) to study the supermolecular structure and thermal behavior of fibrous bionanocomposites, respectively. Both the characterizations positively affect the PCL crystallinity as a result of CMF incorporation. The DSC measurements showed the highest crystallinity (70.11%) at 1.5 wt.% CMF incorporation. The effect of CMF addition on the hydrophilicity of PCL was also investigated by contact angle measurement, where a decreasing trend in contact angle was observed upon CMF loading. Moreover, in vitro degradability of the bionanocomposite nonwoven mats was studied in PBS solution. The rate of degradation was enhanced in the presence of CMF. Moreover, tensile mechanical analysis was carried out and CMF inclusion had a reinforcing impact on electrospun PCL. The highest modulus (19.17 ± 0.8 MPa) and ultimate tensile strength (UTS) (4.45 ± 0.32 MPa) were achieved at 1.5 wt.% CMF addition to PCL. [ABSTRACT FROM AUTHOR]