The invention relates to an on-line colorimetric pH measuring instrument for water vapor detection of a power plant, and belongs to a water quality chemical analysis instrument. The instrument comprises a multi-path sample injection valve, an overflow device, a water shortage detection device, a channel selection valve, a peristaltic metering pump I, a peristaltic metering pump II, a mixer, an automatic thermostat, a photometer, a pH 6.86 standard liquid barrel, a pH 9.18 standard liquid barrel, a pH 10.0 standard liquid barrel and a phenolphthalein indicator barrel. The instrument has the advantages that the non-traditional glass electrode is used as the pH sensor, the glass electrode and corresponding accuracy influence factors are eliminated, the photometer with high stability and accuracy is used for measurement, the measurement accuracy and reliability are greatly improved, the workload of instrument maintenance personnel is reduced, and the method is a novel method for online measurement of the pH of a steam-water system of a power plant. According to the characteristic of slow change of water quality pH of a power plant, time-sharing measurement of more paths of water samples can be expanded.