Silver nanoparticles doped in polyvinyl alcohol (AgNps/PVA) were synthesized via polymer-promoted reductive reaction of AgNO3 and PVA under time-dependent exposure to UV radiation. The AgNps/PVA composites were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, UV–Vis spectroscopy, and transmission electron microscopy to describe the structure, nuclearity, and distribution of Ag Nps within the PVA matrix. The UV–Vis spectrum of AgNps/PVA exhibited a broad surface plasmon absorption around 425–443 nm which originated from the formation of Ag NPs. Surface analysis by XPS indicated that the Ag NPs were grown solely on the PVA surface at UV exposure time of 2 h (2.0AgNPs/PVA). Increasing the UV exposure time to 4 h will cause the transformation of metallic nanosilver to oxidized nanosilver. UV–Vis absorption spectra were in situ recorded to follow the synthesis of Prussian blue (PB) on 2.0AgNPs/PVA (PB@2.0AgNPs/PVA). The colloidal dispersion of 2.0AgNPs/PVA in an acidic medium containing free Fe(III) ions and potassium hexacyanoferrate(III) revealed an additional band centered at 720 nm due to the intermetal charge-transfer absorbance of the polymeric Fe(II)-C-N-Fe(III) of the PB@2.0AgNPs/PVA nanocomposite. Control experiments were shown to involve a spontaneous electron transfer reaction between 2.0AgNPs/PVA and Fe(III) ions, with a concomitant decomposition of hexacyanoferrate(III) and formation of PB was observed. Moreover, IR gave clear cut evidence for the synthesis of PB@2.0AgNPs/PVA from the appearance of a band for the cyano group at 2090 cm−1.