We report the site-selective α-aryloxyalkyl C-H cyanation and allylation of aryl alkyl ethers using an acridinium photocatalyst with phosphate base under LED irradiation (456 nm). Oxidation of the aryl alkyl ether to its corresponding radical cation by the excited stated photocatalyst allowed facile deprotonation of the ArOC(sp)-H bond to afford an α-aryloxyalkyl radical, which was trapped with sulfone substrates, resulting in expulsion of a sulfonyl radical and formation of allylated or cyanated products.