The paper describes the fabrication and chemical applications of polymer microchannel chips, with special reference to in situ observations of the chemical/physical processes occurring in polystyrene microchannel chips, including those in microchannel-microelectrode/microheater chips. On the basis of absorption/fluorescence microspectroscopy and microelectrochemistry techniques, we show some characteristic features of liquid/liquid extraction, electrochemical responses, and photochemical/electrochemical/thermal synthetic reactions in microchannel chips.