In this work, La0.1Bi0.9-xEuxFeO3 compounds were prepared by solid-state reaction. The phase relation at room temperature was investigated by X-ray powder diffraction. A rhombohedral (R3c) phase exists for x≤0.05; for 0.08≤x≤0.12 a pseudo-R3c phase is found; for x≥0.15 it is an orthorhombic (Pbnm) phase, while the distortion of the Pbnm phase was observed for the composition range of 0.15≤x≤0.20. Magnetic measurements indicate that weak ferromagnetism exists in all the compounds, and for the compounds with x≤0.20 the magnetic moment has the maximum value at x=0.12. The composition dependence of dielectric constant was investigated at room temperature. The relationship between the structure and the physical properties was discussed.