In this paper, we propose a method based on 3-D electromagnetic simulations, for the characteristic impedance extraction of transmission lines employed in TRL calibration, focusing on lines integrated in silicon technologies. The accuracy achieved with TRL calibrations using the proposed characteristic impedance extraction is benchmarked versus conventional approaches, with an emphasis on aluminum pads structures operating in the (sub) millimeter-wave range. The proposed method proves to be insensitive to common sources of error (i.e., large pad capacitance and inductive pad-to-line transitions), which affect the accuracy of characteristic impedance extraction based on measurements, especially as the testing frequency increases. First, direct on-wafer TRL calibrations are performed on uniform CPWs (i.e., with no pads discontinuities) to demonstrate how the proposed method performs as good as the calibration comparison method and outperforms calibration transfer approaches. Finally, the method is applied to a nonuniform CPW-based calibration kit, demonstrating how the proposed method provides accurate results, improving the calibration quality that can be achieved using the calibration comparison method when inductive pad-toline transitions are present.