The effect of liquid additives such as alcohol and glycol on the ultrafine grinding of limestone was investigated by using a vibration rod mill. Liquid additives used in the present work were three alcohols and two glycols with different alkyl groups. The experiments were carried out by a batch operation, and the change in specific surface area of limestone with grinding time was measured by BET adsorption method. The behavior of methanol molecules added as a additive was traced by monitoring the temperature and pressure in the grinding pot during grinding. The results showed that the alcohols and glycols promote ultrafine grinding of limestone, and that the maximum specific surface area of limestone obtained with additives is proportional to the amount of additive. The stepwise addition of a small amount of additive was more effective rather than adding the whole amount at once in increasing the grinding rate of limestone. It was also found that the degradation of crystal structure of limestone was controlled by the addition of alcohol. The grinding status of limestone could be traced by monitoring the temperature in the grinding pot, and the measurement of pressure change in the grinding pot revealed that the additive molecules are chemisorbed on the fresh surface of limestone created by the grinding.