Microstructural features and electrophysical parameters of a number of solid solutions based on PbTiO3 are investigated. Solid solutions (Pb1–3/2x + z/2Nd x )(Ti1–y–zMn y Inz)O3 and Pb1–xCa x Ti1–y(W1/2Co1/2) y O3 with extreme values of the mechanical Q-factor and electromechanical anisotropy are chosen as the objects of investigation. The ferro-piezoceramic samples are obtained through conventional sintering and hot pressing. X-ray structural and microstructural studies are performed, and the complex elastic, dielectric, and piezoelectric parameters of experimental samples are measured. The frequency dependences of complex parameters of the experimental samples have been studied at frequencies of up to 40 MHz. It is established that the extreme values of the mechanical Q-factor and piezoelectric anisotropy of the investigated PbTiO3-based solid solutions are due to microstructural features associated with the technological regimes of ferropiezoceramic fabrication.