Two novel materials based on periodic mesoporous organosilica (PMO) with cationic amine-bridged ligands, (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride (PMO-STPA) and bis(3-triethoxysilylpropyl)amine (PMO-TEPA), were synthesized in this work to obtain materials with reverse-phase/strong anionic exchange mixed-mode or strong anionic exchange retention mechanism, respectively. The resulting materials were comprehensively characterized and showed functionalization with cationic amine-bridged ligands, and values of surface areas characteristic of mesoporous materials (higher than 100m/g). These materials were evaluated for the off-line solid-phase extraction (SPE) of a mixture of six phenoxy acid herbicides (fenoprop, mecoprop, dichlorprop, 2-(4-chlorophenoxy)propionic acid (4-CPPA), 2-(3-chlorophenoxy)propionic acid (3-CPPA), 2-phenoxypropionic acid (2-PPA)) from water samples previous to their analysis by CE with diode-array detection using a dual chiral selector system (20mM of heptakis(2,3,6-tri-O-methyl)-β-CD (TM-β-CD) and 7mM of (2-hydroxypropyl)-β-CD (HP-β-CD) dissolved in 50mM phosphate buffer, pH 7.0) which enabled the simultaneous enantiomeric separation of the six phenoxy acid herbicides in 11min. SPE parameters were optimized and recoveries obtained for PMO-STPA and PMO-TEPA sorbents were compared. Under the optimized conditions, it was demonstrated that using 100mg of PMO-STPA sorbent, a maximum preconcentration factor (PF) of 1500 was achieved with 750mL of standard solution, allowing recoveries between 75.5 and 112.2%, with good repeatability (RSD=1.9-8.7%, n=6). Analytical characteristics of the method were evaluated in terms of precision, linearity and accuracy with method quantitation limits (MQL) between 0.4 and 14.3μg/L. The developed method was applied to the analysis of river samples and effluents from wastewater treatment plants, with recoveries ranging from 78.3 to 107.5%.