The goal of this paper is to study the characteristics of PEDOT:PSS thin films and the effects of varying the processing parameters on the structure, functionality, and surface wetting of spun-on and spray-on PEDOT:PSS thin films. PEDOT:PSS is a polymer mixture, which is electrically conductive and transparent and, therefore, is an attractive material for some optoelectronic applications, such as organic and perovskite solar cells. In this work, the films are fabricated using spin coating (a lab-scale method) and spray coating (an up-scalable method). The effects of spinning speed, drying time, and post-annealing temperature on spun-on samples and the effects of the substrate temperature and number of spray passes (deposition layers) on spray-on samples, as well as the effect of precursor solution concentration on both cases are investigated. Various characterization tools, such as AFM, SEM, XRD, confocal laser scanning microscopy (CLSM), and electrical conductivity measurements are used to determine the film roughness, thickness, structure, and morphology. The solution precursor physical data, such as contact angle on glass substrates, viscosity, and interfacial tension, are also obtained within a practical range of temperatures and concentrations. It is found that in both spin and spray coating routes, only well-controlled operating conditions result in the formation of conductive and defect-free PEDOT:PSS films. The formation of PEDOT:PSS thin films with small grains composed of PEDOT forming the core of the grains and PSS forming a shell or coating, which are evenly distributed in a PSS-rich matrix, is favored. Conditions leading to the above-mentioned electrically conductive scenario are identified. Other topics, such as the formation of defects and dewetting, are also elucidated. (C) 2015 Elsevier B.V. All rights reserved.