For second-order nonlinear optics, a supramolecularly ordered non-centrosymmetric structure is required. Additionally, well-ordered organic semiconducting thin films possess superior electronic properties compared to their amorphous counterparts. Herein, we firstly highlight that the design of nonlinear molecules and their functionalization for good molecular orientation (e.g., H-bonding) is an important method in which to induce supramolecular ordering during subsequent growth. Secondly, we demonstrate a range of growth strategies (e.g., oblique-incidence molecular beam deposition, hot-wall deposition) for the growth of molecularly ordered thin films. Thirdly, we discuss various organic supramolecularly ordered material systems (4-[trans(pyridin-4-ylvinyl)] benzoic acid, 5-bromo-5′-formyl-2,2′-bithiophene-4-nitrophenyl hydrazone, tris(8-hydroxyquinoline) aluminum) and observe the effects of molecular orientation on their nonlinear optical and optoelectronic properties.