The piezoelectric poly(vinylidene fluoride) (PVDF) surface possessing low surface energy was modified by the ion-assisted-reaction (IAR) method for the application of thin film speaker. The IAR-treated hydrophilic PVDF surface was investigated using atomic force microscopy and x-ray photoelectron spectroscopy. The adhesion strength between various types of electrodes and the film was dramatically improved due to the hydrophilic functional groups, such as –C–O–, –(C=O)–, –(C=O)–O–, and so forth. A durable loudspeaker film was fabricated by enhancing the adhesion between the screen-printed poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) and the modified PVDF films. The PVDF speaker film with the PEDOT/PSS electrode showed higher durability, flatter sound pressure level characteristics, and easier processability compared to metals or indium tin oxide electrodes.