This chapter has two objectives: (1) to present the micro-mechanics model of Piezoelectric Fiber-Reinforced Composites (PFRCs) and illustrate some of its advantages and (2) to analytically study the impacts of normal/shear initial stresses and rotation on energies carried by different reflected/transmitted waves at the interface of two dissimilar PFRCs. Numerical studies are performed on PFRCs comprised of PZT-5A-epoxy combination and CdSe-epoxy combination, which are modeled employing Strength of Materials (SM) technique with Rule of Mixtures (RM). Some electro-mechanical advantages of PFRC over monolithic piezoelectric materials are demonstrated. Due to incidence of a quasi-longitudinal (qP) wave, three reflected/transmitted waves, viz. quasi-longitudinal (qP), quasi-transverse (qSV), and electro-acoustic (EA) waves are generated in the PFRCs. The propagation directions of all reflected/transmitted waves are graphically demonstrated. The closed-form expressions of amplitude ratios of all reflected/transmitted waves are derived utilizing appropriate electro-mechanical boundary conditions. As the amplitude ratios cannot be used exclusively to validate the numerical results, the expressions of energy ratios of all reflected/transmitted waves and interaction energy are derived, which exhibit the influence of existing parameters, and the law of conservation of energy is established. This work presents a novel effort to develop a connection between deriving the PFRC’s micro-mechanical model and analyzing the wave reflection/transmission phenomenon in it.