A sensitive method for the determination of vanadium in coal fly ash by electrothermal atomic absorption spectrometry is described. Vanadium is separated using a monothio β-diketo liquid chelating exchanger (LCEH) in chloroform medium. The conditions of separation of vanadium i.e., pH, solvent, kinetics of extraction and the effects of various ions have been studied. The instrumental conditions, graphite furnace programme have been optimized. The precision and accuracy of the method were investigated. The detection limit was found to be 0.58 ng. The accuracy of the method has been demonstrated using a reference sample and recovery of spiked vanadium to the fly ash sample digests.