Polymer‐based composites are used for wound healing applications. This work aims to prepare an inorganic‐polymer nanocomposite based on bentonite, poly(vinyl alcohol), and bacterial cellulose by electrospinning for wound healing. The nanocomposite is synthesized using a solution intercalation technique, with 1–2 wt% nanobentonite concentration variation. The effects of commercial and laboratory‐synthesized nanobentonite as well as the extract of the green walnut shell (EGWS) are examined and characterized by different techniques. The addition of nanobentonite increases the average size of fibers and tensile strength up to 200 nm and more than 15 MPa, respectively, due to the presence of hydrogen bonding formed between the nanobentonite sheets and polymer matrix. By the addition of synthetic nanoclay and EGWS, moderate elongation and strength are achieved. The hydrophilicity shows a decreasing trend up to 2 wt% of commercial nanobentonite; however, the laboratory‐synthesized nanobentonite is not significantly effective. Effects of extracts on the viability of cultured human adipose tissue–derived mesenchymal stem cells (ADSCs) are quantitated, where the samples containing 1–2 wt% of commercial nanobentonite have less toxicity than others. Antibacterial activity is tested against both Escherichia coli and Staphylococcus aureus bacteria according to the agar diffusion test for 72 h, in which EGWS‐based mats exhibit strong antimicrobial activity.