At present, viologen-based compounds can undergo reversible chemical/physical changes under external stimuli such as light and electricity. This makes these compounds have potential applications in smart windows, displays, and sensors. In order to obtain such materials, three viologen-POM inorganic–organic hybrid compounds have been successfully synthesized by a hydrothermal method, namely {[Cu2(cybpy)8(α-P2W18O62)2}·18H2O (1), (Hbpy)·(cybpy)·[H4(α-P2W18O62)]}·32H2O (2) and {(Hcybpy)2(β-Mo8O26)}·2H2O (3) (cybpy·Br = 1-cyclobutylmethyl-[4,4′]bipyridinyl-1-ium bromide, bpy = 4,4′-bipyridine). Three compounds exhibit good discoloration behaviors under various external stimuli, especially under the stimulation of X-ray, UV, electricity, and organic amines. In addition, in order to promote the compounds in the actual production of more applications, they were doped into the polymer matrix to construct hybrid films, which not only have the same response to external stimulation but also increase the repeatability of the photochromic process. Moreover, 1–3 powder samples in ethanol solution were ultrasonic treated and deposited on filter paper, which can be successfully used in erasable inkless printing.