The coupling of aryl iodides with alcohols under mild conditions has been explored using self-assembled octanuclear copper clusters as catalysts. Reactions involving tetrahydrofurfuryl alcoholwere typically complete in 4−8 h at 110 °C using an oil bath or 1−3 h with microwave heating.High yields of alkyl aryl ethers were obtained with catalyst loadings as low as 0.4 mol % cluster.