The permittivity of a material is an important parameter to characterize the degree of polarization of a material and identify components and impurities. This paper presents a non-invasive measurement technique to characterize materials in terms of their permittivity based on a modified metamaterial unit-cell sensor. The sensor consists of a complementary split-ring resonator (C-SRR), but its fringe electric field is contained with a conductive shield to intensify the normal component of the electric field. It is shown that by tightly electromagnetically coupling opposite sides of the unit-cell sensor to the input/output microstrip feedlines, two distinct resonant modes are excited. Perturbation of the fundamental mode is exploited here for determining the permittivity of materials. The sensitivity of the modified metamaterial unit-cell sensor is enhanced four-fold by using it to construct a tri-composite split-ring resonator (TC-SRR). The measured results confirm that the proposed technique provides an accurate and inexpensive solution to determine the permittivity of materials.