Semiconductors are the key materials in many of our modern day devices, such as sensors, integrated circuits, energy harvesting devices, optoelectronics and so on. However, apart from two known elemental semiconductors that are silicon and germanium, we have been using many of the synthesized ones since the microelectronic revolution known as invention of transistor. Numerous compound semiconductors since then have been synthesized, grown, deposited or simply fabricated by numerous processes in the scientific community. To avoid associated chemical disposals or keep safe from toxic or combustible gas usages in any semiconductor fabrication facilities, many researchers choose physical vapor deposition as the simplest method. One of such processes is called Close-Spaced Sublimation (CSS), which is a kind of thermal evaporation by nature. This chapter would give a comprehensive outline on CSS as one of the most advantageous semiconductor deposition processes for many compound semiconductors having relatively low evaporation temperature. Cadmium telluride (CdTe) is one of the examples utilized for solar cell absorber materials since the early 1980s using CSS technique. Therefore, growth of CdTe thin films by CSS and its utilization in thin film solar cells will be discussed to comprehend the ultimate benefits of the close-spaced sublimation (CSS) process.