The growing environmental and sustainability challenges necessitate the development of alternative renewable feedstocks to relieve human’s heavy reliance on the finite fossil fuels. In this context, cellulosic biomass emerges as a promising candidate for chemical production due to its largest natural abundance among all biomass resources. In addition, cellulose molecular chains exhibit well-defined chemical structure, making them attractive for chemical and material syntheses as building blocks. However, conventional thermochemical processes such as pyrolysis and gasification for converting cellulose into bulk chemicals suffer from high energy intensity, heavy emissions, process complexity, low product selectivity, and limited yield, undermining their scalability and economic feasibility. Recent developments in electrified heating technologies and reactor designs offer unprecedented opportunities to decarbonize thermochemical cellulose upcycling while improving the overall reaction performance. To this end, we developed a model cellulose-to-levoglucosenone conversion strategy with high yield and fast processing rate using spatiotemporal Joule heating. While most studies focused on the furan-based pathways for cellulose conversion, here we unlock the potential of a complementary route for value-added solvent and drug precursor syntheses. Specifically, we designed a multi-zone Joule-heated reactor for programmable heating with highly tunable residence time, temperature pattern, spatial distribution, among others. These features critically allow us to modulate the reaction kinetics, heat transfer, and mass transport, tailoring the physicochemical property and reactivity differences of various species in the system. Our concept can be extended to efficient conversion of cellulose into other valuable anhydro-sugars and lignin upcycling.