Water-soluble dipyridinium thiazolo [5,4-d]thiazole (TTz) compounds are incorporated into inexpensive poly(vinyl alcohol) (PVA)/borax films and exhibit fast (<1 s), high-contrast photochromism, photofluorochromism, and oxygen sensing. Under illumination, the films change from clear/yellow TTz 2+ to purple TTz •+ and then blue TTz 0 . The contrast and speed of the photochromism are dependent on the polymer matrix redox properties and the concentration of TTz 2+ . The photoreduced films exhibit strong, nearinfrared light (1000−1500 nm) absorbances in addition to visible color changes. Spectroscopic ellipsometry was used to establish the complex dielectric function for the TTz 2+ and TTz 0 states. Incorporating non-photochromic dyes yields yellow-to-green and pink-to-purple photochromism. Additionally, when illuminated, reversible photoactuation occurs, causing mechanical contraction in the TTz-embedded films. The blue film returns to its colorless state via exposure to O 2 , making the films able to sense oxygen and leak direction for smart packaging. These films show potential for use in self-tinting smart windows, eyeglasses, displays, erasable memory devices, fiber optic communication, and oxygen sensing.