A lack of knowledge about the features of Nafion confined to ultrathin films at the interface has motivated additional examinations to promote the performance of polymer electrolyte membrane fuel cells (PEMFCs). In this work, we demonstrated the utilization of practical film-forming technique inkjet printing to fabricate a Nafion ultrathin film less than 10 nm thickness. However, the well-known "coffee-ring" effect caused poor quality of the printed pattern, which has restricted its application. This report describes a systematic investigation of necessary parameters such as ink concentration, substrate type, pitch, and offset for printing processes. Furthermore, post-treatment in an ethanol vapor atmosphere exhibited a significant effect on flattening and homogenizing the film surface morphology. Results show that the well-distributed Nafion ultrathin film modified by ethanol vapor annealing manifested much-improved proton conductivity.