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The current work describes the synthesis of a new polyHIPE‐like sulfonated poly(styrene‐co‐n‐acylglycerol) and its use as an efficient heterogeneous catalyst to convert oleic acid into methyl oleate in esterification reactions. This new environmentally friendly polymer incorporates n‐acylglycerol macromonomer as a versatile strategy for glycerol valorization. Macroporous micrometric polymer particles are synthesized through suspension polymerization process without using porogenic agents. polyHIPE‐like copolymers formed with different feed compositions of styrene and n‐acylglycerol are chemically modified via sulfonation reactions to form a highly efficient catalyst for esterification of oleic acid to methyl oleate, exhibiting conversions lying in the interval from 52% to 96%, depending mainly on the amount of n‐acylglycerol macromonomer into the copolymer chains. The experimental results indicate the great potential of this new heterogeneous catalyst based on modified poly(styrene‐co‐n‐acylglycerol) to be successfully employed in esterification reactions of vegetable oils intended for the production of long chain alkyl esters of carboxylic acids, widely used as biofuels. [ABSTRACT FROM AUTHOR]