Polyoxometalates (POMs) have been used for spectrophotometric determinations of silicon and phosphorus under acidic conditions, referred to as the molybdenum yellow method and molybdenum blue method, respectively. Many POMs are redox active and exhibit fascinating but complicated voltammetric responses. These compounds can reversibly accommodate and release many electrons without exhibiting structural changes, implying that POMs can function as excellent mediators and can be applied to sensitive determination methods based on catalytic electrochemical reactions. In addition, some rare-earth-metal-incorporated POMs exhibit fluorescence, which enables sensitive determination by the enhancement and quenching of fluorescence intensities. In this review, various analytical applications of POMs are introduced, mainly focusing on papers published after 2000, except for the molybdenum yellow method and molybdenum blue method.