Dry reforming of biogas is referred as an attractive path for sustainable H2 production over decades. Meanwhile, in the Malaysian context, the abundance of palm oil mill effluent (POME) produced annually is deemed as a potential renewable source for renewable energy generation. Conventionally, nickel (Ni) is the most common catalyst used in the industrial-scale dry reforming of methane (DRM) to yield H2, but it is subject to the drawbacks of sintering and deactivation after a long reaction time at high temperatures (>500 °C). Therefore, this work aims to provide an insight on the feasibility of the application of modified Ni-based catalysts in DRM, specifically in the economic and environmental aspects. From the benchmarking study of various Ni-based catalysts (e.g., bimetallic (Ni-Ce/Al2O3), alumina support (Ni/Al2O3), protonated titanate nanotube (Ni-HTNT), and unsupported), the Ni-MOF catalyst, notably, had proven its prominence in both economic and environmental aspects on the same basis of 10 tonnes of H2 production. The MOF-based catalyst not only possessed a better economic performance (net present value 61.86%, 140%, and 563.08% higher than that of Ni-Ce/Al2O3, Ni/Al2O3, and Ni-HTNT) but also had relatively lower carbon emissions (13.18%, 20.09%, and 75.72% lower than that of Ni/Al2O3, Ni-HTNT, and unsupported Ni). This work also accounted for 3D printing technology for the mass production of Ni-MOF catalysts, where the net present value was 2 to 3% higher than that of the conventional production method. Additionally, sensitivity analysis showed that the H2 price has the greatest impact on the feasibility of DRM as compared to other cost factors.