In this study, the synthesis of the Aurivillius Ca1-xBi3+xNdTi4-xMnxO15 (CBNTMx), where x is 0, 0.2, and 0.4, was carried out using the hydrothermal technique. The X-ray diffraction (XRD) data showed that the polar orthorhombic structure in space group of A21am was adopted by all powder samples. All samples possessed anisotropic plate-like particle shapes, and the particle size increased with increase in x value. The phase transition temperature (Tm) is decreased by the ionic substitution owing to the decrease in orthorhombic distortion reflected by the reduction of orthorhombicity. Relaxor-ferroelectric behavior was observed for CBNTM0.4 because of its strong frequency dispersion, while CBNTM0 and CBNTM0.2 only showed a diffused-phase transition (DPT) indicated by the broad dielectric constant at the transition temperature (Tm). The electrical conductivity exhibited an enhancement at higher x value since the ionic substitution with acceptor Mn3+ ions introduced the charge carrier in the lattice. Similarly, the reduction of optical band gap energy from 3.43 eV for the parent CBNTM0 to 2.75 eV and 2.71 eV for CBNTM0.2 and CBNTM0.4, respectively, was described as the contribution of the lower energy level of Mn 3d orbital than that of Ti 3d in the conduction band and also the less distorted structure.