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In this paper, we address the subject of converting cornstalk into simple sugars with high-pressure nonequilibrium plasma. The process complies with the green chemistry principle and, thus, does not involve the use of any chemical agents required by conventional methods. In addition, the process avoids the oxidation or combustion of cornstalk. High-pressure nonequilibrium plasma was generated using a dielectric barrier discharge device, which was designed and built in the laboratory. The results show that, under the following conditions, the conversion rate of cornstalk was 75.65%, with a sugar selectivity of 32.11%: a temperature of 80degC, atmospheric pressure of 90 kPa, N2 flux of 1.3 L/min, saturation vapor's flux of 0.13 L/min, discharge gap distance of 1.66 mm, voltage of 3.0 kV, and discharge duration of 120 min. The results demonstrate the feasibility of converting cornstalk, which is conventionally considered to be waste, into sugars under environmentally friendly conditions.