Green electrospinning technique was employed to prepare chloroacetated natural rubber (CNR)/poly(vinyl alcohol) (PVA) nanofiber films by varying the addition of PVA in the range 2.5-55 wt % followed by encapsulation of 2.5 wt % fumed silica (FS). In this study, the risk of using organic solvents was eliminated using CNR in latex. The encapsulated electrospun fiber mats showed a fairly homogenous composition with enhanced water absorption ability of 703.54%+/- 33.95%. The FS improved the interfacial adhesion and contributed to enhancing the intermolecular interaction between the two polymers. The mean diameter of the nanofibers decreased from 64.0 +/- 19.0 to 41.0 +/- 13.0 nm and significant improvement in the hydrolytic and enzymatic degradation rate was observed implying that FS can facilitate the degradation rate. Furthermore, loading of PVA and encapsulation of FS resulted in an improved stiffness of CNR at room temperature and storage modulus increased to 2.48 and 2.12 MPa, respectively. (c) 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46432.