The invention discloses a water quality online monitoring system which comprises a pump, a liquid storing unit, a reacting-detecting unit and a multi-pass direction selecting valve. The multi-pass direction selecting valve is provided with a sample introducing passage, a reagent passage, an analytical passage and a common passage communicating with the liquid storing unit; the reacting-detecting unit is composed of a light source, a reacting-detecting chamber, a detector and an analytical device; one end of the reacting-detecting chamber communicates with the analytical passage, and the other end is connected with a valve. The invention further discloses a water quality online detecting method. The monitoring system has the advantages of simple structure, high measurement accuracy and high response speed. Furthermore, the system can measure a plurality of parameters in a water sample, and can be widely applied to the online monitoring of water quality of various water sources, such as domestic sewage, industrial sewage, stream water, river water, etc.