The invention discloses a single crystal graphene pn node and a preparation method thereof. The modulated and doped graphene pn node is prepared according to the method which comprises the following steps of 1, annealing a copper foil substrate; 2, growing a sub-monolayer intrinsic graphene island on the surface of a copper foil by taking methane as a carbon source; 3, cleaning a growing system by using inert gas; 4, taking acetonitrile steam as a nitrogen-containing carbon source and growing nitrogen doped graphene on the boundary of the intrinsic graphene island; 5, repeating the steps 2, to 4, for at least zero time to obtain the single-level or multi-level graphene pn node; 6, quickly reducing the temperature to stop a growing process; and 7, transferring the graphene pn node which is obtained through modulating, doping and growing onto any target substrate by using polymethyl methacrylate (PMMA) as a medium. The modulated and doped graphene pn node with high quality is obtained by regulating the carbon source in the graphene growing process. The product has very high migration rate and photon to current conversion efficiency; and a transfer characteristic curve of the product has a double-Dirac point, so that the single crystal graphene pn node can be applied to logic devices, such as a phase inverter and a frequency multiplier.