The effects of different types of imperfect interfaces, normal and shear initial stresses and rotation on the reflection and transmission characteristics of plane waves in two dissimilar piezothermoelastic fiber-reinforced composite (PTFRC) half-spaces are analytically studied in this article. The PTFRC structure is modeled employing the Strength of Materials (SM) technique with the Rule of Mixtures (RM) approach. Numerical studies are performed on two distinct PTFRCs comprised of CdSe–epoxy combination and PZT-5A-epoxy combination. Several reasons, like the inevitable presence of interfacial defects because of accumulative damages, have detrimental effects on the life expectancy and efficiency of structures manufactured using smart materials. For the same reasons, the bond between half-spaces is generally not perfect. Thus, the mechanical–electrical-thermally imperfect boundary is classified into seven types, viz. Normal Stiffness Boundary (NSB), Transverse Stiffness Boundary (TSB), Thermal Contact Conductance (TCC), Electrically Imperfect Boundary (EIB), Slip Boundary (SB), Completely Debonded Boundary (CDB) and Welded Contact (WC), which are analyzed individually. Initial stresses and rotation are also considered for making the present model more realistic. The closed-form expressions of amplitude ratios of reflected and transmitted quasi-longitudinal (qP), quasi-transverse (qSV), thermal (T-mode) and electro-acoustic (EA) waves are derived by means of appropriate mechanical–electrical-thermally imperfect boundary conditions. Using these, the energy ratios of all waves along with the interaction energy among various waves are obtained and the Law of Conservation of Energy is validated. Comparative analysis among the Classical dynamical coupled, Lord–Shulman and Green–Lindsay thermoelasticity theories is performed. The influences of the incident angle, imperfect interfaces, rotation, varying magnitudes of normal and shear initial stresses and thermal relaxation parameters on the energy ratios are illustrated graphically. Some special cases exclusive to this study are shown which validate the obtained results with extant literature and possible scientific and engineering applications of the present model are discussed.