A novel time-domain reflectometry technique is developed for detecting the physical structures of transmission lines by using arbitrary waveforms. By discretizing both incident and reflected waves, we formulate the reflection coefficient of a nonuniform transmission line as a polynomial ratio in the Z-transform, wherein the numerator and denominator represent the reflected and incident waves, respectively. A reconstruction scheme is derived to obtain the characteristic impedance profile of a transmission line. Some examples are presented to illustrate the validity of this new technique.