Bronsted acid sites on fluoride-modified AlPO4-Al2O3 (2.5 wt% F; APAl-P-2.5F) catalyst are poisoned by the presence of 2,6-dimethylpyridine (DMPY) and hexamethyldisilazane (HMDS), thus decreasing the catalytic activity for cyclohexene and cumene reaction processes, while the effect of pyridine (PY) was scarce. Besides, the drop in activity for cyclohexene conversion was accompanied by a change in reaction selectivity so that hydrogen transfer sites are much more sensitive to base poisoning (getting greater as the poisoning effect increased) than isomerization sites. Moreover, surface trimethylsilyl (TMS) complexes (formed by covalent reaction of HMDS with surface hydroxyls) decomposed and thus, the activity progressively increased at increasing time intervals, thus reaching greater values (at ca. 4 h) than the unpoisoned APAl-P-2.5F catalyst. So, DMPY was more suitable than PY and HMDS for the poisoning of Bronsted acid sites on APAl-P-F catalyst.