Multiphoton-excited fluorescence (MPEF) is a complementary and useful mode of laser induced fluorescence (LIF) detection in capillary electrophoresis (CE) with advantages of ultra-low mass detectability and spectral excitability.But its currently quite limited by high cost offs laser and end-column detector configuration.In this paper, we demonstrated a novel MPEF detection method for CE based on continuous wave (CW) diode laser of ultra-low cost, instead of expensive fs laser.First, the possibility of CW-based MPEF was theoretically evaluated that indicated that MPEF could be achieved with enough power of CW diode laser.Then a homemade instrument with an end-column detector configuration was developed, which experimentally confirmed CW-based MPEF could be coupled to CE.Features of spectral excitability and capillary size-independence were revealed.Capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) separations of FITC-labeled amino species proved that CW-based MPEF was versatile to micro separations of liquid phase.