A surfactant bound poly (11-acrylaminoundecanoic acid-ethylene dimethacrylate) monolithic column was simply prepared by in situ co-polymerization of 11-acrylaminoundecanoic acid and ethylene dimethacrylate with 1-propanol, 1,4-butanediol and water as porogens in 100 pm id fused-silica capillary in one step This column was used in CEC-atmospheric pressure photoionization (APPI)-MS system for separation and detection of N-methylcarbamates pesticides. Numerous parameters are optimized for CEC-APPI-MS After evaluation of the mobile phase composition, sheath liquid composition and the monolithic capillary outlet position, a fractional factorial design was selected as a screening procedure to identify factors of ionization source parameters, such as sheath liquid flow rate, drying gas flow rate, drying gas temperature, nebulizing gas pressure, vaporizer temperature and capillary voltage, which significantly influence APPI-MS sensitivity A face-centered central composite design was further utilized to optimize the most significant parameters and predict the best sensitivity Under optimized conditions, S/Ns around 78 were achieved for an injection of 100 ng/mL of each pesticide Finally, this CEC-APPI-MS method was successfully applied to the analysis of nine N-methylcarbamates in spiked apple juice sample after solid phase extraction with recoveries in the range of 65-109%