Some solid solutions with the chemical composition KxFeyTi8-yO16 (KFTO) and a hollandite-like structure were successfully synthesized by modified sol–gel method. The obtained powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The ceramic pellets based on KFTO powders were obtained by compressing and sintering at 1080 °C for 4 h. The sinters were characterized by X-ray and impedance spectroscopy. XRD results show that KFTO powders have a mono-phase tetragonal structure at x = 1.4–1.8 and y = 1.4–1.6. However, it was recognized that the hollandite-like phase could be broken during sintering to form TiO2 and Fe2TiO5 crystals distributed throughout the volume of the ceramics. A frequency dependency of dielectric properties for the sinters was studied by impedance spectroscopy. It was found that an increase in the TiO2 (rutile) phase during the sintering contributes to a decrease in dielectric losses. At the same time, the KFTO ceramics with reduced content of potassium had increased permittivity. The contribution of electron-pinned defect dipoles (EPDD) and internal barrier layer capacitance (IBLC) in the permittivity of the obtained ceramics was estimated using the Havriliak–Negami equation. It is shown that the KFTO ceramics have the polydisperse characteristic of dielectric relaxation. The observed grain and grain boundary dipole relaxation times were 1.03 × 10−6 to 5.51 × 10−6 s and 0.197 to 0.687 s, respectively.