Steam reforming of methane is a versatile technology for hydrogen production in oil refinery and fuel cell applications. Using natural gas is a promising method to produce rich-hydrogen gas. Ni@yolk–ZrO₂ catalyst is used to study steam reforming of methane under various GHSVs, steam-to-carbon (S/C) ratio, and its recyclability. The catalyst was characterized using a combination of XRD, TEM, AAS, TPR, TPH, TGA, BET, XPS, and Raman techniques. The catalyst is evaluated on time stream and identify its anti-agglomeration property and coking mechanism. From the characterization of TEM and XPS establish the information of Ni particles mobility in the catalyst, which active metal particle size was controlled under the yolk–shell structure framework. Furthermore, the results from TGA, TPH, and Raman analysis of the used Ni@yolk–ZrO₂ catalyst showed the characteristic of inhibiting formation of highly ordered carbon structure.