An efficient PCl 3 -promoted Friedel-Crafts reaction using esters as both alkylating and acylating reagents has been developed. By using a PCl 3 /I 2 combination, various esters underwent Friedel-Crafts alkylation and acylation reactions with arenes in one-pot, readily producing two kinds of products aromatic ketones and alkyl aromatics by one step in good yields. The Friedel-Crafts alkylation and acylation of arene with 4-formylbenzoate derivatives in one-pot have also been achieved. This novel strategy features high step economy, low-cost, metal-free and simple reaction conditions.