A class of prearomatic carboxylic acid p-quinol ester radical precursors has been developed successfully, which could undergo homolytic cleavage of the para C-O bond of p-quinol esters via pyridine-boryl radical-induced aromatization in the presence of pyridines and diboron reagents, affording the corresponding alkyl radical via decarboxylation from the carboxyl radical in situ. In addition, the prearomatic radical precursors were further applied in radical substitution with phenylsulfonyl compounds and radical self-coulpings. This method not only provides a new approach to the generation of a radical intermediate but also expands the application of boron radicals.