Aromatic sulfonyl halides are readily accessible from many sources. With newly synthesized N-arylphenothiazine catalysts, organocatalyzed photoredox polymerization has been developed with arylsulfonyl halides initiators using white or purple LEDs light sources. This method allows the preparation of poly(meth)acrylates and poly(meth)acrylamides possessing a broad scope of (hetero)aryl chain ends without metal-contamination concern. Investigations such as MALDI-TOF analysis, chain extension, and "ON/OFF" control experiments confirmed the fidelity of the polymer structure and reliability of this method. Moreover, this method facilitates the two-step preparation of brush polymers from polystyrene through an electrophilic aromatic substitution/organocatalyzed photopolymerization sequence.