H2 production through dry reforming of methane (DRM) is a hot topic amidst growing environmental and atom-economy concerns. Loading Ni-based reducible mixed oxide systems onto a thermally stable support is a reliable approach for obtaining catalysts of good dispersion and high stability. Herein, NiO was dispersed over MOx-modified-γ-Al2O3 (M = Ti, Mo, Si, or W; x = 2 or 3) through incipient wetness impregnation followed by calcination. The obtained catalyst systems were characterized by infrared, ultraviolet–visible, and X-ray photoelectron spectroscopies, and H2 temperature-programmed reduction. The mentioned synthetic procedure afforded the proper nucleation of different NiO-containing mixed oxides and/or interacting-NiO species. With different modifiers, the interaction of NiO with the γ-Al2O3 support was found to change, the Ni2+ environment was reformed exclusively, and the tendency of NiO species to undergo reduction was modified greatly. Catalyst systems 5Ni3MAl (M = Si, W) comprised a variety of species, whereby NiO interacted with the modifier and the support (e.g., NiSiO3, NiAl2O4, and NiWO3). These two catalyst systems displayed equal efficiency, >70% H2 yield at 800 °C, and were thermally stable for up to 420 min on stream. 5Ni3SiAl catalyst regained nearly all its activity during regeneration for up to two cycles.