Purpose: The purpose of the article is to investigate the structure and antimicrobial properties of composite nanofibers with silver particles precipitated onto the nanofibers surface. Design/methodology/approach: A solution was prepared in the first place made of the following solvents to fabricate antimicrobial composite nanofibers of polycaprolactone with silver precipitations: formic acid and acetic acid at a rate of 70:30. Then, silver nitrate was introduced into the fabricated solution of the solvents and it was subjected to the interaction of ultrasounds, and after 10 minutes polycaprolactone was added to the solution, and then the solution was mixed for 12 hours and a solution was obtained with a 10% concentration and the mass fraction of 0, 1, 3 and 5% of silver nitrate additives. The solution was forced into a positive voltage electrode placed above a negative voltage electrode; the solution was then subjected to the activity of a strong electrostatic field transforming the solution into micro- and nanofibers. After electrospinning, the fibers obtained underwent the activity of a 2% ascorbic acid solution, by means of which silver was precipitated on the nanofibers surface. Viscosity and electrical conductivity tests were performed of single-component and double-component solutions, of the fibers’ structure in a transmission electron microscope, of the BET, Langmuir specific surface area and DTF porosity with the method of gas adsorption and antimicrobial activity of the nanocomposites produced on the nanocomposites on following bacteria: Staphylococcus aureus, Escherichia coli, Candida albicans. Findings: The use of a formic acid and acetic acid solution at a rate of 70:30 for preparation of a polycaprolactone solution for its electrospinning enables to obtain a non-toxic and fully biodegradable polymer nanofibers of polycaprolactone with PCL/Ag silver precipitations possessing high antimicrobial performance against Gram+, Gram- bacteria and fungi. Practical implications: Antimicrobial composite nanofibers with silver nanoparticles precipitated onto the nanofibers surface can be applied in biodegradable antiseptic dressings in the form of mats or other textiles containing polymer nanofibers of polycaprolactone with PCL/Ag silver precipitations obtained as a result of electrospinning. Originality/value: The research outcomes confirm that it is feasible to manufacture polycaprolactone nanofibers with PCL/Ag silver precipitations possessing high antimicrobial performance against Gram+, Gram- bacteria and fungi.