A novel anionic surfactant bound monolithic stationary phase based on 11-acrylaminoundecanoic acid is designed for CEC. The monolith possessing bonded undecanoyl groups (hydrophobic sites) and carboxyl groups (weak cationic ion-exchange sites) were evaluated as a mixed-mode stationary phase in CEC for the separation of neutral and polar solutes. Using a multivariate D-optimal design the composition of the polymerization mixture was modeled and optimized with five alkylbenzenes and seven alkyl phenyl ketones as test solutes. The D-optimal design indicates a strong dependence of electrochromatographic parameters on the concentration of 11-acrylaminoundecanoic acid monomer and porogen (water) in the polymerization mixture. A difference of 6, 8 and 13% RSD between the predicted and the experimental values in terms of efficiency, resolution and retention time, respectively, indeed confirmed that the proposed approach is practical. The physical (i.e. morphology, porosity and permeability) and chromatographic properties of the monolithic columns were thoroughly investigated. With the optimized monolithic column, high efficiency separation of N-methylcarbamates pesticides and positional isomers was successfully achieved. It appears that this type of mixed-mode monolith (containing both chargeable and hydrophobic sites) may have a great potential as a new generation of CEC stationary phase.