With the fast development and miniaturization of acoustic and electric smart devices, micro and nanoscale piezoelectric semiconductor materials are gradually being used to manufacture information communication, energy conversion, and nondestructive testing technologies. As the core components of the above piezoelectric semiconductor devices, homo- and hetero-junctions have an evident influence on the propagation performance of high-frequency and short-wavelength elastic waves inside the bulk piezoelectric semiconductor materials. Based on the Gurtin–Murdoch theory, a theoretical model of interface effect originating from homo- and hetero-junctions is established to investigate the propagation properties of Love waves in a piezoelectric semiconductor semi-infinite medium considering the electrical open circuit (insulation) and short circuit (metalized ground) surface boundary conditions and biasing electric fields. Four interface characteristic lengths are introduced to describe the electrical imperfect interface of homo- and hetero-junctions, which are legitimately confirmed through comparisons of the dispersion and attenuation curves of Love waves. The influence of homo- and hetero-junctions on the dispersion and attenuation characteristics of Love waves are elaborated in detail. Numerical results show that the interface characteristic lengths are independent of the electrical surface boundary conditions, acceptor and donor concentrations, thickness of the upper piezoelectric semiconductor layer, and biasing electric fields in the piezoelectric semiconductor semi-infinite medium. Moreover, the propagation characteristics of Love waves can be manipulated by changing the biasing electric field parallel to the homo- and hetero-junctions. Since the high-frequency and short-wavelength Love wave is an important class of surface acoustic waves propagating in micro- and nano-scale piezoelectric semiconductor materials, the establishment of mathematical models and the revelation of physical mechanisms are fundamental to the analysis and optimization of the above piezoelectric semiconductor devices.