A calibration method for radio frequency scattering parameter measurement applying three calibrators and measurement structure thereof, comprising a transmission line segment calibrator, an offset series device calibrator, an offset shunt device calibrator and a tested object measuring instrument, wherein the length of the transmission lines for the offset series device calibrator and the offset shunt device calibrator is equal to the one of the transmission line for the tested object measuring instrument such that the offset series device calibrator, the offset shunt device calibrator and the tested object measuring instrument have the identical error boxes, and after having acquired the scattering parameter matrix of the error box by means of the calibration method, it is possible to connect the tested electronic device onto the tested object measuring instrument and perform operations on uncorrected measurement data thereof thereby obtaining the radio frequency scattering parameter of the tested object.