This paper describes ZBLA fluoride glass thin films produced via an inexpensive, low-temperature reactive atmosphere sol-gel approach. Luminescence from erbium at 1.55 μm has been observed in x-ray-amorphous doped films deposited on calcium fluoride, polyimide, sapphire, and silicon substrates. Fluorescence studies of the erbium 4S3/2 → 4I13/2 transition, a characteristic emission for a reduced phonon energy host, were conducted for both sol-gel-derived films and conventionally prepared glass rods. The peak intensity observed from the sol-gel films was blue-shifted by 16 nm with a FWHM value approximately half that measured for the melt-quenched rods. Excitation studies indicate that, unlike conventionally prepared glasses, sol-gel materials suffer from nonradiative relaxation of the 4S3/2 excited state to the 4I9/2 level, where subsequent radiative emission to the 4I15/2 ground state occurs. The proposed source of the quenching mechanism are remnant species inherent to the sol-gel process. While this causes the luminescence behavior of rare-earth-doped sol-gel-derived fluoride materials to be similar to oxide hosts, these remnant species modify the branching ratios, resultantly leading to a novel 824 nm emission when excited at 488 nm.