Furfurylamine is an important furfural-upgrading biobased chemical for the production of pharmaceuticals, biofuels, fibers, additives, polymers, etc. In one-pot reaction system, biomass was tandemly catalyzed to furfurylamine with aluminium-based alkaline-treated graphite (Al-AG) catalyst and recombinant ω-transaminase biocatalyst. Al-AG (3.6 wt%) catalyzed corncob (75.0 g/L) to 110.0 mM furfural at 56.8% yield (based on xylan in corncob) in γ-valerolactone–water (1:4, v:v; pH 1.0) for 40 min at 180 °C. The pH-adjusted corncob-slurry (pH 7.5) containing furfural were catalyzed to furfurylamine at high yield with γ-valerolactone-tolerant Aspergillus terreus ω-transaminase biocatalyst at 35 °C using isopropylamine (3 mol isopropylamine/mol furfural) as amine donor. Such an efficient and sustainable approach for catalytic conversion of biomass to high-value-added biobased furfurylamine was successfully established in tandem reaction with Al-AG and ω-transaminase biocatalyst.