In this work, polyvinyl alcohol (PVA) is chemically bonded to carbon nanoparticles (CNPs) by a very simple and versatile solution casting method. Five different kinds of CNPs/PVA composite films were prepared; 0.5, 1.0, 1.5, 2.0, and 3.0 wt% CNPs dispersed in PVA. The as‐prepared samples were characterized using various characterization techniques. The resulting nanocomposites proved to possess homogeneity and better mechanical, thermal, optical, and flame‐retardant properties than pure PVA. Most of the CNPs with average particle size ≤100 nm were homogeneously dispersed in the PVA matrix showing fluorescence in the violet color zone. The crystallinity of the nanocomposites show a decline in the diffraction intensity as compared to pure PVA which results from the dwelling of CNPs inside the gaps of stacked‐layer chains of PVA. The mechanical properties of nanocomposites indicated enhancement in toughness, elastic modulus and tensile strength with an increase in CNPs contents. The assessment for flame‐retardant properties was carried out through cone calorimetry. The results show a decrease in both total heat release rate (THRR) and peak heat release rate (pHRR) of the resulting nanocomposites as compared to pure PVA. The superior properties of the CNPs/PVA composites stemmed from the good interfacial bonding between the CNPs and PVA matrix.