A report on the evidence for an additional magnetic ordering and magneto-dielectric permittivity with dielectric relaxation besides multiferroic behavior in FeVO4 doped with Te4+ (s = 0) is presented in this manuscript. Synchrotron X-ray diffraction (SXRD) results confirm triclinic crystal structure of Fe1−xTexVO4 (x = 0.025, 0.05, 0.075 and 0.10) samples. Two antiferromagnetic (AFM) transitions similar to FeVO4 at ∼21.86 K (TN1) and 16.03 K (TN2) were observed in all samples. An additional magnetic ordering at relatively higher temperature (TAMO) ∼203 K is observed due to possible V4+ - E• O - Fe3+ superexchange bonds leading to short range magnetic clustering. Evaluated magnetic moments show systematic decrease and the magnetic frustration factors show an increase with the increasing of Te4+ (s = 0) content. Magneto-dielectric studies show stable ferroelectric ordering at spiral magnetic transition (TN2) and the multiferroic order persists to the largest doping of Te (x = 0.10). At ∼203 K (TAMO) large dielectric permittivity (" = 6000) and strong frequency dispersion were observed in the dielectric permittivity ("), loss (tanδ) with and without magnetic field indicating relaxation behavior due to electronic inhomogeneous conduction mechanism within the material in terms of electron hopping between excess oxygen and neighboring transition metals in the form of V4+-E• O -Fe3+. Mossbauer studies confirm local structural correlation with magnetic and ferroelectric ordering.