Reflective-mode step-impedance transmission line based sensors for dielectric characterization of solids or liquids have been recently proposed. In this article, in order to further increase the sensitivity, the sensor is implemented in coplanar waveguide (CPW technology), and this constitutes the main novelty of this work. The sensor thus consists of a high-impedance 90° (or low-impedance 180°) open-ended sensing line cascaded to a low-impedance 90° (or high-impedance 90°) line. The output variable is the phase of the reflection coefficient, which depends on the dielectric constant of the material under test (MUT), the input variable. Placing a MUT on top of the sensing line causes a variation in the effective dielectric constant of the line, thereby modifying the phase of such line. This in turn produces a multiplicative effect on the phase of the reflection coefficient, by virtue of the step-impedance discontinuity. The main advantage of the CPW-based sensor, over other similar sensors based on microstrip technology, is the stronger dependence of the phase velocity of the sensing line with the dielectric constant of the MUT, resulting in sensitivities as high as -45.48° in one of the designed sensors. The sensor is useful for dielectric characterization of solids and liquids, and for the measurement of variables related to changes in the dielectric constant of the MUT (defect detection, material composition, etc.).