The visible light-assisted photocatalysis approach allows more sustainable and atom-economical C–H bond arylation processes. The polymer-based photocatalysts are an attractive choice because of their variable design and development feasibility as well as effective catalytic applications. In the present work, by following the basic principles of green chemistry, we have chosen an environmentally friendly and biologically suitable chemical i.e. Erythrosine B as a unit molecule for the generation of photocatalyst EP (C20H8O5S4). The generation of EP has been performed via a one-pot solvothermal reaction of Erythrosine B with sulfur powder. The structural analysis of the EP evidence the generation of an interesting example 2D-polymeric assembly where disulfide (–S–S–) units are acting as linkers and show high thermal stability up to 800 °C (39.9% left as a residue). The low optical band gap of 2.08 eV and electrochemical band gap of 2.09 eV favors its catalytic applicability. The catalytic investigation reveals excellent applicability of EP in C–H arylation (yield 98.5% & selectivity 99%). [ABSTRACT FROM AUTHOR]