Detection of trace manganese (Ⅱ) ion (Mn) is crucial to water safety. Here, commercially available PS-DVB microspheres were sulfonated and then filled into the SPE column in order to separate Mn from complex matrices. Meanwhile, europium (III) complex was prepared with a simple "one pot" method, and its fluorescence intensity was quenched gradually with the increase of Mn concentration. Europium (III) complex combined with home-made SPE column was utilized for highly selective and sensitive measurement of Mn. The detectable concentrations of Mn can be low as 0.2 μM, which was less than the drinking water guidelines. Consequently, this new method is promising to assess the content of Mn rapidly and accurately in real-world water samples.