In this study, we have investigated the crystal structure of the solid solution of antiferroelectric NaNbO3(NN) with ferroelectric Ba0.9Ca0.1TiO3(BCT), i.e. (1−x)NN- xBCT for 0⩽x⩽1.0 using High-resolution powder x-ray diffraction (HR-XRD) data, dielectric measurements in conjunction with Raman spectroscopic studies. The investigation of long-range structural phase transitions as a function of composition(x) using x-ray diffraction is complemented by short-range structural insights from Raman spectroscopy. The incorporation of BCT disrupts the delicate antiferroelectric ordering of NN and stabilizes various ferroelectric phases with increasing BCT content(x). At x = 0.10, the simultaneous presence of two ferroelectric phases viz., Pmc21 and Amm2, results in a threefold rise in remanent polarization compared to off-boundary compositions. The composition with higher BCT content (i.e. x⩾0.50 ) has shown the anomalous existence of two long-range cubic structures, both of which are characterized by Pm 3¯ m space group. In spite of having a two-phase long-range centrosymmetric structure, we have observed a slim Polarization vs. Electric field(P-E) hysteresis loop for 0.50⩽x⩽0.80 . This contrapositive behavior (i.e. hysteresis loop in a centrosymmetric structure) has been attributed to the correlations among local static polar distortions of rhombohedral type ascertained using Raman spectroscopy. The coexistence of two ferroelectric phases at room temperature(for x = 0.10) and a slim hysteresis loop (for 0.50⩽x⩽0.80 ) make these compositions potential ingredients for applications in ferroelectric memory and energy storage devices.