This paper presents a simple and economical method for preparing durable anti-static functionalized inkjet prints by using P[St-BA-F6]—novel antistatic agents synthesized by an oxidative polymerization of styrene, butyl acrylate, and allyl alcohol polyether F6. The P[St-BA-F6] was characterized by gel permeation chromatography and Fourier transformation infrared spectroscopy. One bath pretreatment solution containing P[St-BA-F6] and pentaerythritol tetraacrylate (PETA) were applied to polyester fabrics before inkjet printing, in order to enhance the color yield and the anti-static properties. The pretreatment conditions, including the concentrations of P[St-BA-F6], curing temperature, and time, were optimized based on inkjet printed polyester fabrics. SEM (scanning electron microscope), XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffractometer), TG (thermogravimetric), and DSC (differential scanning calorimetry) examined the fabrics. The results showed that the treated PET fabrics exhibited good applied performances, such as higher color yield, better dry rubbing fastness, lower electrostatic voltage, and durable anti-static properties, even after washing 10 times. These results can be attributed to alcohol polythene group (F6) and allyl group (PETA). PETA can be cross-linked with P[St-BA-F6] and PET fiber. The thermal stability of the treated fabric was lower than that of the untreated fabric, owing to the presence of resin film on the fiber surface.