A novel method utilizing combination of N, N-dimethylformamide (DMF) and ultraviolet (UV) irradiation to reduce silver (Ag+) ions in situ in ultrafine poly-(l-lactide-co-∊-caprolactone-diOH) (PCLA) fibers was developed. Compared with traditional solvent reduction method, the new method exhibited much higher efficiency. UV–visible spectra indicated that the addition of UV irradiation could shorten the reaction time dramatically. Transmission electron microscope and x-ray photoelectron spectroscopy results demonstrated that the new method had produced a larger number of uniform Ag nanoparticles (AgNPs). After statistical analysis, their mean size was determined as 6.96 nm, which was smaller than that of traditional AgNPs. In addition, as a biodegradable polymer, PCLA was first used to carry AgNPs. It was found that PCLA can be a stabilizing agent of Ag+ ions. Therefore, the formation mechanism of AgNPs with larger number and smaller size can be determined.
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