Hexagonal Lu0.5−x Zr x Sc0.5FeO3 polycrystalline samples are synthesized by conventional solid‐state reaction. Effects of slight Zr4+ ions substitution on the structural distortion and magnetoelectric properties are investigated. The coexistence of Fe2+ and Fe3+ is checked by X‐ray photoelectron spectroscopy (XPS). X‐ray diffraction (XRD) and Raman spectrum (RS) microstructural analysis reveal that all samples are in the hexagonal structure with the polar space group of P6 3 cm. With x increasing slightly, the tilting of FeO5 bipyramids and the bending of rare‐earth atomic layers are suppressed. The Néel temperature T N of antiferromagnetic (AFM) transition is decreased, whereas the weak ferromagnetic (WFM) order is strengthened. The permittivity ε r of the samples is significantly increased. A dielectric anomaly near T N in Lu0.45Zr0.05Sc0.5FeO3 may indicate magnetoelectric coupling. It is attributed to the spin–phonon coupling as is evidenced by the Raman phonon modes. The improvement of dielectricity and magnetoelectric coupling is explained by considering the Dzyaloshinskii–Moriya interaction, structural distortion, and the incremental ratio of Fe2+ ions. These results provide an idea for sensitive control of electric and magnetic properties in related materials.