This chapter provides an overview of the versatile applications and properties of epitaxial ferroelectric materials obtained using the pulsed laser deposition technique. These materials can play a significant role in various electronic and sensing applications or energy harvesting. Materials that are ferroelectric and have a perovskite structure (ABO3 type) show spontaneous polarization that can be changed by an electric field, temperature, mechanical stress, or light. Here, we present results obtained on epitaxial ferroelectric thin films with different compositions, lead-based or lead-free, and the correlation with structural quality of the layers and with different electrostatic conditions induced either by the substrate or by the different dopants. Our studies revealed that the utilization of pulsed laser beam deposition technique is suitable for obtaining ultrathin films depositions with thicknesses measuring less than 5 nm. These results allowed us to reveal the impacts caused by polarization orientation on the band structure or the presence of self-doping phenomena. We also found that the conduction type can be modified by introducing 1% Fe and Nb on PbZrTiO3 (PZT) epitaxial layers. In the last part of this chapter, we report on obtaining of a lead-free epitaxial thin film and its properties in the energy storage field.