Here, we report detailed studies on magnetic phase transitions and magnetoelectric (ME) coupling in Fe_1-xCe_xVO₄ . X-ray diffraction (XRD) and Raman spectroscopic measurements confirm triclinic crystal structure (P-1) with small variation in lattice parameters and Ce incorporation into the FeVO₄ lattice up to 10% of Ce. The presence of local lattice distortions and electronic inductive effect in FeVO₄ between Fe³⁺ and V⁵⁺ ions were found in X-ray absorption near edge structure (XANES) studies due to the presence of Fe³⁺–O–V⁵⁺ linkages. Two antiferromagnetic (AFM) transitions similar to FeVO₄ appear at 21.86 K and 16.03 K, and Ce doping has little effect on the magnetic transitions. ⁵⁷Fe Mössbauer spectroscopic results show the invariance of Fe valance. Low temperature high magnetic field Mössbauer data depicts the presence of spiral AFM order in all the samples. A sharp peak at 16.0 K in dielectric permittivity with minimal suppression due to applied magnetic field is observed indicating the presence of ferroelectricity and magneto-dielectric coupling. Magnetic and ME transitions are almost robust against Ce doping.