Appropriate control of substrate surface properties prior to inkjet printing could be employed to improve the printing quality of fine resolution structures. In this paper, novel methods to fabricate patterned surfaces with a combination of hydrophilic and hydrophobic properties are investigated. The results of inkjet printing of PEDOT/PSS conductive ink on these modified surfaces are presented. Selective wetting was achieved via a two-step hydrophilic–hydrophobic coating of 3-aminopropyl trimethoxysilane (APTMS) and 3M electronic grade chemical respectively on PET surfaces; this was followed by a selective hydrophilic treatment (either atmospheric O2/Ar plasma or UV/ozone surface treatment) with the aid of a Nickel stencil. Hydrophobic regions with water contact angle (WCA) of 105° and superhydrophilic regions with WCA <5° can be achieved on a single surface. During inkjet printing of the treated surfaces, PEDOT/PSS ink spread spontaneously along the hydrophilic areas while avoiding the hydrophobic regions. Fine features smaller than the inkjet droplet size (approximately 55 μm in diameter) can be successfully printed on the patterned surface with high wettability contrast.