Polycrystalline Cr3+ substituted Ba4Zn2Fe36-xCrxO60 (Zn2U) U-type hexaferrite compositions Ba4Zn2Fe36-xCrxO60 (x = 0.0, 0.5, 1.0, 1.5, and 2.0) were fabricated using the sol-gel self-ignition technique. U-type hexaferrite structure was achieved by sintering the powdered samples for 6 h at 1200 °C in a muffle furnace. The phase identification and structural parameters of Zn2U hexaferrites were evaluated by X-ray diffraction peaks of the powdered samples. Lattice parameters (a,c) and unit cell volume decreased upon Cr3+ substitution. The crystallite size was measured between 61 and 57 nm. FTIR spectra revealed the existence of specific absorption (Fe–O) bands at wavenumbers 419 and 539 cm−1. These bands further verify the formation of U-type hexaferrite. SEM micrographs showed the platelet-like morphology of the grains with proper hexagonal structure. X-ray photoelectron spectroscopy (XPS) results confirmed the existence of all metal ions with their corresponding electronic states. The dielectric response of the fabricated Zn2U U-type hexaferrite pellets was investigated at room temperature through a vector network analyzer with a wide frequency band from 1 MHz to 6 GHz. Dielectric constant (εʹ) was increased for the compositions x = 1.0 and 1.5 while dielectric loss (εʺ), tangent loss (tanδ), and ac conductivity (Ϭac) were reduced upon Cr3+ substitution. Single semicircles in the impedance Cole-Cole plots revealed that grain boundaries play a vital role in the conduction process of prepared U-type hexaferrites. Microwave absorption (MW) was improved with Cr3+ substitution. The minimum reflection loss (RL) of −53dB (99.99% MW absorption) at frequency 1.3 GHz was obtained for composition x = 0.5. The dielectric analysis (low losses and high Q-values) of the prepared hexaferrites predicts their appropriate use in high-frequency device applications.