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Boiler scaling was among the major reasons for the frequent occurrence of boiler accidents. By monitoring and controlling the total alkalinity of boiler water, the scaling tendency could be altered, thus the orderly functioning of the boiler could be ensured. However, on-line monitoring and control of the total alkalinity of boiler water was still a difficult issue both at home and abroad. In this paper, a new way to tackle the problem was proposed, in which the total alkalinity of boiler water was indirectly obtained through the on-line measurement of boiler water's pH value and temperature and the boiler pressure. Based on the standard for the total alkalinity of boiler water stipulated in Water Quality Standards (GB 1576-85), an intelligent compound control strategy was adopted to realize the on-line intelligent control of the total alkalinity of boiler water on a 16-bit chip microcomputer-based system. As is shown from the actual operating results, the method of the real-time monitoring and control of the total alkalinity of boiler water in this paper is feasible, the monitoring and control system developed is both reliable in functioning and easy to operate, and relatively better controlling effects have since been achieved.