A direct functionalization of numerous 1,4-quinones with various aryl boronic acids is reported under blue light-emitting diodes (LEDs). This reaction occurs at room temperature in an open flask without any catalysts, base, and oxidants in acetonitrile (ACN) and is scalable in grams. With diverse 1,4-quinones like 1,4-benzo-, naphtho-, anthra-, and 4-bromonaphthoquinones as substrates, facile cross coupling reactions occur with aryl and alkyl boronic acids without assistance from any photocatalysts. 2-Alkylated cyclohexene-1,4-diones were obtained when the 1,4-quinones were reacted with alkyl boronic acids under standard reaction conditions. However, slight warming of the reaction mixture afforded the desired alkylated 1,4-quinones. The reaction is believed to proceed through the blue LED-induced radical formation of the aryl rings assisted by the 1,4-quinones. © 2022 American Chemical Society. All rights reserved.