The invention discloses a novel enrichment hydrogen production process of volatile organic compounds under the action of low-temperature plasmas and hydrophobic silicon dioxide. According to the method, a plasma reactor is filled with the hydrophobic silicon dioxide, so that VOCs (volatile organic compounds) in waste gas are adsorbed and enriched, the VOCs are selectively adsorbed, namely, the hydrophobic silicon dioxide only adsorbs the VOCs and has weaker adsorption capacity for impurities such as aqueous vapor, the plasma reactor is started after adsorption of the hydrophobic silicon dioxide for the VOCs is saturated, the aqueous vapor is decomposed into active radical particles such as OH and H, the active radical particles and the VOCs react under the catalytic action of the hydrophobic silicon dioxide to finally generate clean energy H2, so that the VOCs are purified, and the hydrogen is produced. According to the process, the hydrophobic silicon dioxide serves as an adsorbing agent and a catalyst, the low-temperature plasmas discharge to induce the aqueous vapor to perform reforming reaction, so that the VOCs are efficiently degraded in a low-loss manner, the clean energy H2is generated, and waste is turned into wealth.