X‐parameters provide a powerful and eminently practical solution for interoperable measurement, modeling, and simulation of nonlinear microwave and RF components. Using X‐parameters to do large‐signal measurements has been brought into the spotlight. This paper introduces a new X‐parameter application: measuring large‐signal behaviour of pulse‐compression nonlinear transmission lines (NLTLs). A specially configured Nonlinear Vector Network Analyzer (NVNA) was used to measure the X‐parameters in the frequency‐domain, and then the measured data was transformed into a nonlinear time‐domain waveform. The results show both rise‐time and fall‐time reduction (double‐edge compression) as expected and indicate that this newly developed X‐parameter method implemented with an NVNA could correctly predict NLTLs′ pulse‐compression performance.