In this paper, a novel SrEr2O4 ceramic with relative densities exceeding 96% was synthesized by a conventional solid-state reaction method. Furthermore, investigations of the correlations between its crystal structure, microstructure, and microwave dielectric properties were carried out. Rietveld refinements show that the SrEr2O4 ceramics crystallize in the orthorhombic with the space group Pnam. The SrEr2O4 ceramic sintered at 1575 °C exhibits the good performance of permittivity (εr) = 14.44, quality factor (Q×f) = 23271 GHz, and resonant temperature frequency coefficient (τf) = –21.5 ppm/°C, which is attributed to its high lattice energy, packing fraction, and relative density. In addition, to satisfy the requirement of temperature stability for communication devices, near-zero τf value is obtained by adding CaTiO3 at the cost of a small quality factor loss. The SrEr2O4 + 1.25 wt% CaTiO3 composite exhibits decent properties with εr = 18.57, Q×f = 19940 GHz, and τf = +3.99 ppm/°C, making it an ideal candidate for microwave band applications.