Efficient metal-free electrocatalysts as the environmentally friendly and inexpensive products are critical for oxygen reduction reaction (ORR) benefitting the commercial viability of fuel cells. Herein, a new “partial surface dissolution” (PSD) approach was proposed to prepare biomass-based porous carbon for ORR. Cotton cellulose was partially dissolved and swelled in the NaOH/urea mixture where NaOH was used as an activator and urea was acted as a nitrogen resource, followed by carbonization at temperatures of 800℃ for the preparation of the hierarchically interconnected porous carbon. The specific surface area of the nitrogen-doped porous carbon is 1921.33 m2/g, which can offer more electrocatalytic active sites for the synergistical enhancement of ORR. In 0.1 M KOH solution under oxygen saturation, the initial potential and the half-wave potential (E1/2) of porous carbon were 0.912 V (vs. RHE) and 0.82 V (vs. RHE), respectively, comparable to platinum carbon catalysts. In addition, the porous carbon also exhibited a high limiting current density of −5.2 mA cm−2, especially stability of larger than 96.4% retention after 10000 s. This research offers a new method to prepare the production of cheap and efficient metal-free electrocatalysts for fuel cell.