In the last few decades extensive attention has been given to the advancement of metal-catalysed C-H functionalization. Despite the steady progress in the process, atom economical techniques are being explored using varieties of metal catalysts. Many of these metal-based catalytic systems have the major drawback of limited catalyst recyclability. Contrary to the formerly mentioned catalytic system, heterogenous polymer and nanoparticle-based catalysts have shown promising results. These heterogenous catalysts are largely comprising of transition metal complexes and nanoparticles embedded within a polymer matrix. They provide a variety of advantages over homogeneous metal-based catalysts, such as easily available raw materials, ease of separation, thereby enhancing recyclability, etc. The focus on the heterogenous nanoparticle catalytic systems for C-H functionalization reactions is due to their unique size-dependent properties, which have a direct impact on the process selectivity. Herein, a comprehensive overview on the potential for greener and more sustainable C-H functionalization processes using heterogeneous polymer and nanoparticle catalysts is provided. In addition, selective functionalization, improving properties and sustainability in chemical processes of such heterogeneous catalytic systems are assessed. These lead to the conversion of the “unactivated” C(sp²)-H and C(sp³)-H bonds found in easily accessible hydrocarbons into useful compounds, thereby providing environmentally friendly methods for industrial applications in pharmaceuticals, agrochemicals, materials science, and in the formation of fine chemicals.

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