(Bi1/2Na1/2)(Fe1/3Mn1/3W1/3)O3 is a new complex perovskite compound synthesized by a solid-state method. A preliminary structural study using the X-ray diffraction (XRD) pattern shows the monoclinic symmetry of the material. The scanning electron microscope (SEM) micrograph shows the dense microstructure or morphology of rectangular shape grains of different dimensions. The purity and elemental composition of the compound were obtained by energy dispersive X-ray (EDX and EDS) spectrum. The analysis of frequency and temperature-dependent relative dielectric constant (εr) impedance and ac conductivity (σac) predict the presence of Maxwell-Wagner type of dielectric dispersion and thermally activated relaxation mechanism. In-depth analysis of impedance and associated factors reveals that they are substantially dependent on temperature and have a significant link with their microstructures. Similar to semiconductors, the nature of impedance spectra displays a negative temperature coefficient of resistance behavior. The electric polarization hysteresis loop shows the ferroelectric behavior and explores the possible applications. The band gap (Eg) is found to be 2.40 eV using the UV-visible spectrum, appropriate for solar and optoelectronic applications. The value of super-capacitance is 58.96 F/g, applicable for an electrode material supercapacitor application. The behavior of leakage currents has also been investigated and found that conduction has been identified as a space-charge conduction mechanism. We are very interested in designing and manufacturing novel dielectric ceramics because of the rising need for the miniaturization of electronic components and the flexibility of applications. Sensors, actuators, transducers, and capacitors are among the most prevalent applications of such types of materials.