Organic semiconductors as active materials in thin-film electronic devices such as alkynes, heterocycles, dyes, ferrocenes, spiranes, or porphyrins, with special geometries and certain electronic molecular parameters, which possess nonlinear optical (NLO) properties and offer several major advantages over their inorganic counterparts, are presented in this chapter. There are a number of simple and versatile techniques that can be employed for the deposition of these important classes of materials. The matrix-assisted pulsed laser evaporation (MAPLE) technique provides advantages with regard to making organic films of different morphologies on different types of substrates. New insights into the crystallization growth mechanisms in MAPLE-deposited conjugated polymer films, which realize the connection between the structure and the carrier transport properties, are discussed herein. Second harmonic generation (SHG) capabilities of the thin films were also investigated.