A photoinduced arylation of N-substituted acridinium salts has been developed and has exhibited a high functional group tolerance (e.g., halogen, nitrile, ketone, ester, and nitro). A broad range of well-decorated C9-arylated acridinium-based catalysts with fine-tuned photophysical and photochemical properties, namely, excited-state lifetimes and redox potentials have been synthetized in a one-step procedure. These functionalized acridinium salts were later evaluated in the photoredox-catalyzed fragmentation of 1,2-diol derivatives (lignin models). Among them, 2-bromophenyl substituted N-methyl acridinium has outperformed all photoredox catalysts, including commercial Fukuzumi's catalyst, for the selective CβO-Ar bond cleavage of diol monoarylethers to afford 1,2-diols in good yields.