A facile and green synthetic strategy is developed in this paper for the construction of an efficient catalyst for the industrially important carbon dioxide reforming of methane, which is also named the dry reforming of methane (DRM). Through controlling the synthetic strategy and Ni content, a high-performance Ni@CeO₂ catalyst was successfully fabricated. The catalyst showed superb efficiency for producing the syngas with high and stable conversions at prolonged operating conditions. Incorporating Ni during the ceria (CeO₂) crystallization resulted in a more stable structure and smaller nanoparticle (NP) size with a more robust interaction with the support than loading Ni on CeO₂ supports by the conventional impregnation method. The H₂/CO ratio was almost 1.0, indicating the promising applicability of utilizing the obtained syngas for the Fischer–Tropsch process to produce worthy chemicals. No carbon deposits were observed over the as-synthesized catalyst after operating the DRM reaction for 50.0 h, even at a more coke-favoring temperature (700 °C). Owing to the superb resistance to coke and sintering, control of the size of the Ni-NPs, uniform dispersion of the active phase, and potent metal interaction with the support, the synthesized catalyst achieved a magnificent catalytic activity and durability during serving for the DRM reaction for extended operating periods.