Scheelite-structure tungstates with unique structural features and excellent luminescence possess promising applications, such as light-emitting diodes (LEDs), scintillators, and displays. The controllable growth of high quality and uniform composition thin films mounted on cheap substrates is a key factor to realize the above commercial applications, however, which is also a big challenge due to the difficult stress release stemming from intrinsic lattice mismatches. Here, we employed the simple and composition-controlled polymer-assisted deposition (PAD) method to successfully obtain a series of high quality and well-proportioned BaWO4:Eu3+ (BWOE) thin films with red emission. Screening out the unbound freedom metal ions by poly(ether imide) (PEI) and ethylene diamine tetraacetic acid (EDTA), the firmly bound metal ions (Ba2+, W6+ and Eu3+) in polymer solution were applied to accurately control the chemical composition and effectively governed the release of stress during the growth process of BWOE thin films. Furthermore, XRD, SEM and EDS mapping detections evidently authenticated the quasi-single crystallinity, uniform morphology and well-distributed composition of as-grown thin films. Additionally, excited by 250 nm light, these thin films could efficiently produce the red emission, peaked at around 612 nm originated from the 5 D0 → 7 F2 transition of Eu3+. Moreover, the optimal doping concentration of thin films was confirmed to be 9% and corresponding Commission International de l'Eclairage (CIE) chromaticity coordinate was (0.618, 0.365), which evidently implied the excellent color rending index. Therefore, this work highlights the rather superior PAD method to prepare uniform and high-quality BWOE thin films, which can be expanded toward the other photoelectric devices including white lighted-emitting diodes, scintillators, displays, and photoelectric detectors.