Structure, morphology, and electrical properties of 10 mol% of Nb2O5‐activated yttrium barium titanate (BT) Ba(60‐z)Ti(40‐x)NbzYxO3 (BTY10Nb10), barium titanate (BT), and 10 mol% of Y2O3‐activated BT were explored with calcination and sintering temperatures of 1000°C at 8 h and 1200°C at 6 h, respectively. The thermogravimetric and differential scanning calorimetry (TG–DSC) analysis reported that the total weight loss and residual mass of BT at 1300°C were 16.8 and 83.2%, respectively. The X‐ray diffraction (XRD) pattern confirmed that BTY10Nb10 ceramics containing the BaNbO3 phase were developed. A Raman band of BT at 307 cm–1 unveiled a blue shift slightly for BTY10 to 298 cm–1 and for BTY10Nb10 to 306 cm–1. Average pore area of the ferroelectric BTY10Nb10 was found to be 6.96 nm for the total scanning electron microscopy (SEM) image area of 20.31 nm. Formation of BT nanorods analyzed from transmission electron microscopy (TEM) has been reported in three samples that regulate surface roughness. Moreover, Nyquist diagram of BTY10Nb10 shows two overlapping semicircles as a function of frequency. Nanorod structures led to change the morphology and surface roughness. Recoverable energy storage density and energy storage efficiency were estimated as 2.63 µJ/cm3 and 57%, and BTY10Nb10 ferroelectric showed potential for energy storage applications due to changes in surface morphology and porosity.