Conformations of diethoxymethane (DEM) were studied using matrix isolation infrared spectroscopy. DEM was trapped in an argon matrix using an effusive source maintained at various temperatures: 298, 388, and 430 K. The elevated temperatures were used to increase the population of the higher energy conformers in the matrix. As a result of these experiments, infrared spectra of the ground, G(+/-)G(-/+)(tt), and higher energy conformers, G(+)G(-)(g(+)t), G(+)G(-)(g(-)t), and TG(+/-)(tt), of DEM are reported, for the first time. The experimental studies were supported by ab initio computations performed at B3LYP level, using a 6-31++G** basis set.