The sustainable upgrading of biomass-derived furfural (FF) to γ-valerolactone (GVL) via catalytic transfer hydrogenation (CTH) offers a green alternative to conventional hydrogenation routes. Herein, monometallic Cu-BTC, Ni-BTC, and Co-BTC metal–organic framework catalysts were synthesized by a solvothermal method and evaluated for FF conversion. Ni-BTC and Co-BTC outperformed Cu-BTC due to their favorable redox properties and stronger surface acidity, enabling efficient activation of the hydrogen donor and promoting ring-opening and lactonization steps. To further enhance catalytic efficiency, bimetallic NiCo-BTC catalysts with varying Ni/Co ratios were developed. All bimetallic catalysts showed superior performance, with 0.50NiCo-BTC achieving complete FF conversion and a high GVL selectivity and yield of 89% at 200 °C after 24 h. Physicochemical analyses (TEM, XPS, XANES, and NH₃-TPD) revealed that synergistic Ni–Co interactions and enhanced acidity are key factors governing activity. Time-resolved product analysis confirmed a sequential reaction pathway via furfuryl alcohol. The catalyst also exhibited good reusability and structural stability, underscoring the potential of MOF-based catalysts for sustainable biomass valorization.