Unsymmetrical di-and triarylmethanes are usually synthesized by metal-catalyzed cross-coupling or Friedel–Crafts arylation utilizing multistep harsh response circumstances with pre-functionalized beginning supplies. These response protocols use pyrophoric supplies akin to Grignard reagents, metallic hydrides, and poisonous, hazardous, and problematic solvents like benzene, DMF, and THF. This impacts the response mass effectivity, and atom financial system and produces vital environmental wastes leading to a excessive E-factor. Instead, herein, utilizing an affordable, commercially accessible Brønsted acid-catalytic system (pTSA·H2O)/HFIP, we describe a one-pot three-component strategy for the synthesis of unsymmetrical polyarylated alkanes from renewable feedstock chemical compounds. In comparison with standard routes, we prevented utilizing any pyrophoric reagents, metallic catalysts, poisonous solvents, or Grignard reagents and report many examples which are troublesome to entry utilizing the reported strategies. Calculation of various inexperienced metrics (atom financial system (95%), atom effectivity (84.5%), response mass effectivity (77.1%), and E-factor (1.26 kg kg−1 of the product with out solvent restoration and 0.32 kg kg−1 of the product contemplating solvent restoration) indicated the greenness of the described protocol. The developed technique may be scaled up and was utilized for a brief and environment friendly synthesis of a phenanthrene-based anti-breast most cancers agent, which diminished the traditional six-step cross-coupling strategy to the one step Friedel–Crafts strategy. Additionally, the strategy was utilized for the late-stage functionalization of assorted pure merchandise akin to thymol, menthol, and eugenol and the used HFIP was recovered, highlighting the suitability of the strategy for industrial functions.