The invention belongs to the field of sensing, and particularly relates to a super-sensitive gas sensor based on a graphene D-shaped optical fiber. According to the invention, external voltage is applied through a gold-graphene-gold heterojunction structure to adjust the Fermi level of graphene; by applying external voltage, the Fermi level of the graphene is adjusted to a position close to a Dirac point, and when sensed gas molecules are adsorbed to the graphene, the carrier concentration of the graphene is changed, so that tiny change of the Fermi level is caused. As the Fermi level of the graphene is close to a Dirac point, a four-wave mixing signal of the graphene D-shaped optical fiber excited by input pump light is most sensitive to response of external sensing molecules, and the sensing sensitivity is optimal at the moment. According to the invention, the interaction between an input optical signal and an external sensing molecule is remarkably enhanced, the size is small, the structure is simple, the sensing sensitivity reaches a single molecule level, an all-fiber structure is adopted, the optical fiber sensing and communication network can be conveniently accessed, and rapid real-time monitoring is realized.