A new series of layered perovskite-like oxides Bi3−xNdxTi1.5W0.5O9 (x = 0.25, 0.5, 0.75, 1.0) was synthesized by the method of high-temperature solid-state reaction, in which partial substitution of bismuth (Bi) atoms in the dodecahedra of the perovskite layer (A-positions) by Nd atoms takes place. X-ray structural studies have shown that all compounds are single-phase and have the structure of Aurivillius phases (APs), with close parameters of orthorhombic unit cells corresponding to space group A21am. The dependences of the relative permittivity ε/ε0 and the tangent of loss tgσ at different frequencies on temperature were measured. The piezoelectric constant d33 was measured for Bi3−xNdxTi1.5W0.5O9 (x = 0.25, 0.5, 0.75) compounds of the synthesized series.