The solid-phase extraction of several polyphenolic compounds with different silica hydride-based stationary phases, as well as an unmodified type-B silica, has been investigated. In particular, the propensities of these stationary phases to extract the selected polyphenolic compounds in the batch-binding mode in the presence of 100% methanol or 50% (v/v) aqueous/methanol solvents have been examined. In addition, the zeta-potential values of these different sorbents have been determined in the same solvent compositions. The results indicated that the batch-extraction behaviour of these polyphenolic compounds with the type-B silica, unmodified silica hydride, the Diamond Hydride™ particles, silica hydride particles modified with immobilized phenyl groups or with other non-polar ligands of larger steric size, such as bidentate octyl, bidentate octadecyl, or cholesteryl groups, did not overall correlate with the particle’s zeta-potential values. However, these results indicated that the selectivity attributes in solid-phase extraction procedures of different types of silica hydride materials with polyphenolic compounds can be differentiated from experimental data acquired with small quantities of structurally related test analytes under aqueous normal-phase conditions solely from physical measurement methods, such as static batch-extraction measurements and associated GS–qMS methods of analysis.