Cellulose, which accounts for more than half of the carbon content in plants, has become a popular feedstock for biofuel production. In this work, direct electricity generation from dissolved cellulosic biomass in an alkaline fuel cell is explored without energy‐intensive process. The effect of different cellulose dissolution solvents on the electricity production is investigated. Results show dissolution treatment can remarkably affect the fuel cell performance. When NaOH/urea/thiourea is chosen as a solvent, the specific capacity of cellulose is about sixfold higher than that using only NaOH as solvent. The limiting current density and the maximum power density reach 0.85 mA cm−2 and 0.07 mW cm−2, respectively. This power density surpasses those of any existing biotic or abiotic designs. Electrochemical characterizations demonstrate that the remarkable activity improvement towards the cellulose oxidation reaction in NaOH/urea/thiourea aqueous solution is due to the lower charger transfer resistance and higher energy transfer efficiency.