The design of novel heterogeneous catalysts with multiple adjacent functionalities is of high interest to heterogeneous catalysis. Herein, we report a method to obtain a majority of bifunctional acid–base pairs on SBA15. Aniline reacts with SBA15 by opening siloxane bridges leading to N-phenylsilanamine–silanol pairs. In contrast with ammonia treated surfaces, the material is stable under air/moisture. Advanced solid state MAS NMR (2D ¹H–¹H double-quantum, ¹H–¹³C HETCOR) experiments and dynamic nuclear polarization enhanced ²⁹Si and ¹⁵N spectra demonstrate both the close proximity between the two moieties and the formation of a covalent Si–N surface bond and confirm the design of vicinal acid–base pairs. This approach was successfully applied to the design of a series of aniline derivatives of bifunctional SBA15. A correlation between the substituent effects on the aromatic ring (Hammett parameters) with the kinetics of a model Knoevenagel reaction is observed.