Biobased furfurylamine (FAM) is a versatile platform molecule for producing additives, pharmaceuticals, and pesticides. Recombinant E. coli HNND-AlaDH was created by co-expressing L-alanine dehydrogenase (AlaDH) and mutated Aspergillus terreus ω-transaminase (HNND), aiming to convert furfural (FUR) into FAM using inexpensive L-alanine and isopropylamine as mixed amine donors. In ChCl:FA:OA (10 wt%), pineapple peel, bagasse, barley shell, peanut shell, and corn stalk could be efficiently transformed into FUR under 170 °C for 10 min. Pineapple peel produced a high titer of FUR (183.3 mM). Additionally, the viscosity, surface tension and polarity of ChCl:FA:OA were explored. The biomass-derived FUR was fully transformed to FAM by HNND-AlaDH with amine donor (1:1:1 of L-Ala/isopropylamine/FUR mol/mol/mol) within 300 min. Accordingly, the FAM productivity was 0.58 g/(g xylan in pineapple peel). This chemobiocatalytic strategy established through the combination of chemocatalysis and biocatalysis could be applied to convert renewable biomass into valuable organic amines.