New methods for the preparation of silver nanoparticles/polymer nanocomposite materials by thermal cationic polymerization of ε-caprolactone (ε-CL) or α-pinene oxide (α-PO) at room temperature (RT) and under air were developed. The new initiating systems were based on silanes (Si), starch nanocrystals (StN) and metal salts. Excellent polymerization profiles were revealed. It was shown that silver nanoparticles (Ag(0) NPs) were in situ formed and that the addition of StN improves the polymerization efficiency. The as-synthesized nanocomposite materials contained spherical nanoparticles homogeneously dispersed in the polymer matrices. Polymers and nanoparticles were characterized by gel permeation chromatography (GPC), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-vis spectroscopy. A coherent picture of the involved chemical mechanisms is presented.