A metal-free oxidative decarboxylation reaction of propiolic acids mediated by hypervalent iodine(III) reagents is described. This decarboxylative C–O bond-forming reaction used a combination of (diacetoxyiodo)benzene and aromatic, heteroaromatic or aliphatic propiolic acids to give the corresponding α-acetoxy ketones. Preliminary mechanistic studies based on both DFT calculations and high-resolution mass spectroscopy (HRMS) suggested that the reaction proceeded through decarboxylation to form a propargyl iodide intermediate. This reaction provides an attractive alternative to existing methods for the exclusive synthesis of α-acyloxy ketones.