We present here a novel nano-channel confined biomimetic nanozyme/bioenzyme system, which is prepared by co-immobilizing polyoxometalates (vanadomolybdophosphoric heteropoly acid, PMoV₂) and glucose oxidase (GOx) in the nano-scale channel of core-shell mesoporous silica (CSMS) microspheres. The biomimetic dual-enzyme nanoreactors (CSMS@PMoV₂@GOx) is used for producing long-lasting chemiluminescence (CL) emission. With glucose and luminol in the reaction mixture, hydrogen peroxide (H₂O₂) is formed in mesoporous channels by GOx catalysis and then is consumed immediately by PMoV₂ to induce CL emission. Confined in nano-size channels of CSMS materials, the biomimetic cascade reactions can induce a long-lasting CL emission with a flat period over 12 h. The proposed CSMS@PMoV₂@GOx system has excellent reproducibility and storage stability, and has been applied for glucose sensing in human serum samples with satisfactory accuracy. Our study provides a new glow-type CL system based on nanozyme/bioenzyme cascade reactions confined in nano-scale channels of CSMS microspheres, and will also shed a light on potential application of functional polyoxometalates immobilized in mesoporous materials, which would be of great value in various fields including bioassays and heterogeneous catalysis.