This article proposes a method based on the use of a slotted rectangular waveguide (SRW) for determining the complex permittivity of materials under test (MUTs). Because the slots are nonradiating and the electric field between the two slots is the strongest, the MUTs can be put through the slots and partially filled in the SRW for measurements. The network parameters of the loaded segment of the SRW are evaluated directly via the line-network-network (LNN) self-calibration technique without needing to obtain the error coefficients of the test fixtures first. The LNN technique requires the measurement of an empty SRW and measurements of the SRW loaded with an MUT at three different positions. The mode matching method is used to determine the complex permittivity of the MUT, which is partially filled in the SRW. The proposed method is suitable for the measurements when there are a large number of MUTs to be measured or an MUT need to be measured many times. The simulation and measurement results show the validity, accuracy, and repeatability of the proposed method.