A site selective, metal‐free C(sp3)−H sulfonylation of 1,2,3,4‐tetrahydroacridines is reported using sulfonyl hydrazides as sulfonyl source in the presence of a combination of tetrabutylammonium iodide (0.2 equiv.) and tert‐butyl hydroperoxide (1 equiv.). This reaction was extended for the 2,3‐dihydroacridin‐4(1H)‐ones via oxidative desulfonylation. Both sulfonylation and desulfonylation steps were achieved in good to excellent yields with broad substrate compatibility.