The porous carbon (bacterial cellulose (BC)-activated carbon (AC)(BA)) prepared via two-step activation of bacterial nanocellulose by treatments with potassium hydroxide (KOH) and then phosphoric acid (H3PO4) solutions showed superior adsorption properties and effective performance as catalyst support. BC-AC(BA) had an open and interconnected multi-porous structure, consisting of micropores (0.23 cm3/g), mesopores (0.26 cm3/g), and macropores (4.40 cm3/g). The BET surface area and porosity were 833 m2/g and 91.2%, respectively. The methylene blue adsorption test demonstrated that BC-AC(BA) was superior in its mass transfer rate and adsorption capacities. Moreover, BC-AC(BA) modified by H3PO4 treatment showed a significant enhancement of catalytic performance for dehydration of ethanol. At the reaction temperature of 250–400 °C, 30P/BC-AC(BA) gave ethanol conversion at 88.4–100%, with ethylene selectivity of 82.6–100%, whereas, high selectivity for diethyl ether (DEE) at 75.2%, at ethanol conversion of 60.1%, was obtained at the reaction temperature of 200 °C.