The invention provides a centrifugal microfluidic chemical luminescence immunoassay disc and its working method. The centrifugal microfluidic chemical luminescence immunoassay disc comprises an injection port, a first reagent port, a detection chamber and a waste liquid chamber. The valve controls the communication between the detection chamber and the waste liquid chamber. The valve comprises a curved channel formed in the disc. The minimum rotation radius R1 of the channel and the maximum rotation radius R2 of the detection chamber are related as follows: R1-R2<0. The invention has the advantages of stability, reliability, high efficiency and rapidity.