Co-W-promoted NiAl2O4 nanocatalyst with various amount of tungsten (0, 1, 3, and 7 wt.%) was fabricated via hybrid sol-gel-plasma method. The nanocatalysts were evaluated by XRD, FESEM, EDX, BET, and FTIR analyses. The samples were utilized in CO2/O-2 reforming of methane to syngas. EDX results proved the existence of all the applied elements in synthesis. FESEM and BET results illustrated that tungsten addition led to lower surface area, larger particle size, and roughly worse particles scattering. Therefore, Co-NiAl2O4 (NCW0A) presented higher yield; however, yields were reduced for the other samples due to the covering impact of tungsten. As a result of time on streams performance (2880 minutes and at 750 degrees C), the 7 wt.% tungsten promoted sample exhibited stable but lower yield (Y-H2 = 64%). Moreover, NCW1A exhibited more stable and higher yield than NCW0A. Optimum operating parameters were obtained as GHSV = 24 l/g(cat).h, CH4/CO2 = 1, and CH4/CO2/O-2 = 1/1/0.08. TG-DTG, EDX, and FESEM analyses were applied for the used samples. TG-DTG graphs demonstrated that by rising of tungsten loading, lighter and lower amount of coke was formed. Some agglomerations were observed in the EDX images of NCW0A and NCW1A while lower agglomeration was found for the tungsten-rich sample. Carbon fiber formation was detected in the FESEM images of the used NCW0A while for the others, amount of the deposited coke and carbon fibers decreased.