Using standard low-temperature (<300 °C) plasma-enhanced chemical vapor deposition (PE CVD) technology, films of a Si(Er): H were obtained that emitted light in the neighborhood of 1.54 µm at room temperature. The Er source was the specially synthesized fluorine-containing metallorganic complex Er(HFA)3·DME where HFA=CF3C(O)CHC(O)CF3 and DME=CH3OCH2CH2OCH3, which possesses a low transition temperature to the gas phase (of order 100 °C) at working pressures (0.1–0.5 Torr) for the PE CVD method. Distinctive features of the photoluminescence spectrum of a-Si(Er):H were investigated in the range 0.5–1.7 µm for T=77 and 300 K. The presence of photoconductivity in the synthesized films is evidence of their satisfactory electronic quality.