The demand for reconfigurable millimetre-wave (mm-Wave) components based on highly anisotropic liquid crystals (LC) is higher than ever before for the UK and worldwide. In this work, 60 GHz investigation on a bespoke shielded coplanar waveguide (SCPW) phase shifter structure filled with 16 types of microwave-enabled nematic LCs respectively indicates that the patterns of the device’s figure-of-merit (FoM, defined as the ratio of maximum differential phase shift to maximum insertion loss) reshuffle from those of the characterised LC materials’ FoM (defined as the ratio of tunability to maximum dissipation factor). To be more specific, GT7-29001- and MDA-03-2838-based phase shifters exhibit the highest FoM for devices, outperforming phase shifters based on GT5-28004 and TUD-566 with the highest FoM for materials. Such a mismatch between the device’s FoM and LC’s FoM implies a nonlinearly perturbed wave-occupied volume ratio effect. Furthermore, the relationship between insertion loss and the effective delay line length is nonlinear, as evidenced by measurement results of two phase shifters (0–π and 0–2π, respectively). Such nonlinearities complicate the established FoM metrics and potentially lead to a renewed interest in the selection and material synthesis of LCs to optimise reconfigurable mmWave devices, and promote their technological exploitation in phased array systems targeting demanding applications such as inter-satellite links and satellite internet.