The present work is aimed to improve the performance of Ni‐based catalysts for biogas dry reforming by adding a second non‐noble metal (Fe, Co, Cu) into a previously studied mesoporous Ni‐CaO‐ZrO2 nanocomposite. Biogas was simulated with equivalent methane and carbon dioxide for the dry reforming reaction. X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), N2 adsorption, temperature‐programmed reduction (TPR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) measurements were taken to characterize the structural and textual properties of the bimetallic catalysts as well as the accumulated carbon deposition. The addition of Fe leads to a less ordering growth of mesopores of Fe‐Ni‐CaO‐ZrO2 sample, and the existence of Cu results in a relatively larger portion of free NiO in Cu‐Ni‐CaO‐ZrO2. Compared with Fe and Cu, the presence of Co could efficiently form a beneficial dual metal effect and enhance the strong metal support interaction between Ni and CaO‐ZrO2, thus enhancing the activity and stability of the catalyst in biogas dry reforming reaction.