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The C2Π-X2Π(0,0) band of AgO has been reinvestigated by laser induced fluorescence spectroscopy with a spectral resolution of ～0.02 cm-1.The AgO molecules are produced by discharging a gas mixture of O2/At with silver needle electrodes in a supersonic jet expansion.By employing a home-made narrowband single longitude mode optical parametric oscillator (SLM-OPO) as the laser source,high-resolution spectra of the C2Π-X2Π(0,0) band have been recorded for both 107Ag16O and 109Ag16O isotopologues.The spectroscopic constants of the C2Π state are consequently determined,with the 109Ag16O one being reported for the first time.The nature of the spin-orbit coupling effect in the C2Π state is proposed to be due to state mixing with the nearby repulsive 4Σ-and 4Π states.