The application discloses a preparation method of a vanadium-doped carbon composite back contact layer and application of the vanadium-doped carbon composite back contact layer in preparation of a cadmiumtelluridesolar cell. The method comprises the following steps: firstly, performing a coordination reaction on a vanadium source compound and a carbazolemonomer to obtain a vanadium-doped carbazolepolymer; secondly, dissolving and coating the polymer on a surface of a cadmiumtelluride light absorption layer; and thirdly, performing gradient annealing treatment on the polymer to convert the polymer into the vanadium-doped carbon composite back contact layer in situ. During the gradient annealing process, selective rupture of coordination bonds of the polymer is caused, and vanadium ions released from the polymer preferentially diffuse along cadmiumtelluride grain boundaries to form a local P + Doped region; At the same time, the polymer main chain is carbonized to form a dense conductive network similar to graphene. The prepared back contact layer has high conductivity and high efficient hole transport function, can effectively control the contact potential barrier between the cadmium telluride light absorption layer and the back electrode, and improves the injection and collection efficiency of holes.