In this paper, we present a two-port on-wafer scattering parameter measurement method to tackle the issue of crosstalk between probes. The proposed method treats the crosstalk separately during the system calibration and the device measurement stages, because the crosstalk during these stages is often different due to changes in the measurement conditions after the probes have been calibrated. For example, devices under test (DUTs) and calibration standards are often situated on different substrates, or, the distance between probes during calibration is different from that during DUT measurement. Based on this concept, we develop a new error model in which the crosstalk is treated as a standalone two-port error network in parallel with the two-port calibration standards or DUTs. The two-port crosstalk error generated during probing, ECT, is removed in the system calibration and corrected during the measurement of the DUT by using a dummy pair of open-circuit standards that are fabricated on the same substrate as the DUT. Since the crosstalk is corrected while measuring the DUT, rather than during system calibration, we call this method "calibration on the fly" (COF). The method is demonstrated using measurements of a 10-dB attenuator between 140 GHz and 220 GHz.