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An experimental analysis of the Bi0.90Tb0.1Fe0.90Mn0.1O3 system synthesized via the solid‐state method is presented in this report. UV–visible measurements are carried out and a smaller bandgap (i.e., semiconductor‐type behavior) is obtained. The structural phase of the present system is analyzed with X‐ray diffraction and neutron diffraction measurement. Structural‐phase analysis reveals that the system contains two nuclear phases (rhombohedral structure [R3c space group] with orthorhombic [Pn21a space group]). Moreover, also more bending in the bond angle is found, and the existence of a magnetic phase with a nuclear phase for the Bi0.90Tb0.1Fe0.90Mn0.1O3 system is also confirmed by neutron diffraction. The magnetic moment versus temperature (M–T) curve demonstrates that the system's Néel transition temperature is at 568 K. The magnetization data show enhancement in the magnetic property by displaying the weak ferromagnetic‐type behavior at room temperature in the magnetic field versus magnetic moment (M–H) curve as compared to the parent compound. From dielectric measurement, the dielectric constant increases while the loss decreases. [ABSTRACT FROM AUTHOR]