The alcoholysis of acetyl chloride, propionyl chloride and butyryl chloride with some alcohols in acetone and toluene has been investigated by means of calorimetric measurements. Furthermore a comparison with benzoyl chloride has been made. In the case of i-propanol in acetone, a smaller rate constant has been found for the alcoholysis of propionyl chloride than for butyryl chloride. In contrast to this, almost equal rate constants have been determined for the reactions of these acyl chlorides with n-propanol and ethanol. In toluene, the rate constants for the reaction of acetyl chloride with all considered alcohols has the highest values under similar conditions but then decrease from acetyl chloride to butyryl chloride. The observed differences and the changes of rate constants are discussed and compared with literature data.