Poly(vinyl alcohol) (PVA), a high‐consumption polymer, is currently facing the problem of overcapacity. The development of modified PVA with novel properties is an alternative way to solve this problem. In this work, glyoxylic acid was used as a bridging agent to indirectly bond europium ions to PVA molecule chain. The luminescence properties of the modified PVA materials were investigated by adjusting the reaction conditions such as pH value, heating treatment methods, reaction temperature, and doping concentration. Upon excitation at 394 nm, a strong and tunable luminescence is achieved due to the existence of both blue emission from Eu2+ and red emission from Eu3+. The luminescence properties are explained based on the reduction of Eu3+, the existence form of europium ions, and the arranged regulation of PVA molecules. The modified PVA materials have potential applications in the fields of displaying and lighting if their luminescence properties are further improved in the future.