Hexagonal ferrites have drawn significant attention due to a broad range of telecommunication and stealth technology applications. β-Type hexagonal ferrites are rarely used in various technological applications. In the current work, Nd3+ substituted polycrystalline β-type hexagonal ferries with composition LiFe11-x NdxO17 (x = 0.0–0.04, ∇ x = 0.01) were prepared using the sol-gel method. All prepared samples were sintered at 1000 °C for 4 h. The influence of Neodymium (Nd3+) on its structural, electrical, and dielectric properties was investigated. Lattice parameters (a, c) and Vcell increased with varying Neodymium substitution levels. The crystallite size was measured in the range of 38–42 nm. Fourier Transform IR (Infrared) spectroscopy exposed the presence of two spectral bands at 416 to 449 cm−1 and 449 to 489 cm−1. XPS (x-ray photoelectron spectroscopy) analysis verified the presence of metal ions and their chemical states in all prepared samples. The dielectric constant, loss, tan δ, and σac (ac-conductivity) decreased by increasing Nd3+ content. Jonscher's power law explains the conduction mechanism of charge carriers in all fabricated samples. The influence of relaxation time and grain boundaries on the electrical characteristics of prepared nanomaterials was investigated by impedance analysis. SEM (scanning electron microscopy) confirms the successful formation of β-hexaferrite nanomaterials. A minimum reflection loss of −32.08 dB was observed at 1.5 GHz for the x = 0.04 sample. This minimum reflection loss evidenced the novelty of the research and suggested their usefulness in high-frequency microwave applications. All samples investigated in this research work are suitable for high-frequency applications, multilayer chip inductors, and EM interference shielding.