(Bi0.5Na0.5)0.94Ba0.06TiO3 dense ceramics were obtained from autocombustion sol-gel synthesized nanopowders and sintered at 1050 °C for 1–2 h for the study of the electromechanical anisotropy. Measurement of the complex impedance spectrum was carried out on thin ceramic disks, thickness-poled, as a function of the temperature from 16 °C up to the vanishing of the electromechanical resonances at the ferroelectric to relaxor transition near 100 °C. The spectrum comprises the fundamental radial extensional mode and three overtones of this, together with the fundamental thickness extensional mode, coupled with other complex modes. Thermal evolution of the spectrum shows anisotropic behavior. Piezoelectric, elastic, and dielectric material coefficients, including all losses, were determined from iterative analysis of the complex impedance curves at the planar, thickness, and shear virtually monomodal resonances of disks and shear plates, thickness-poled. d33 was measured quasi-statically at 100 Hz. This set of data was used as the initial condition for the optimization of the numerical calculation by finite elements of the full spectrum of the disk, from 100 kHz to 1.9 MHz, to determine the thermal evolution of the material coefficients. An appropriate measurement strategy to study electromechanical anisotropy of piezoelectric ceramics has been developed.