AbstractSurface‐enhanced infrared absorption spectroscopy (SEIRA) of methanol, ethanol, 1‐propanol, and 2‐propanol in thin films on planar silver halide (AgX) fibers under slow N2 flow using 1 sec scans reveals structure in absorbance–time plots. The absorption intensities show extra enhancements (3×) in the absorbance (OH stretch) ascribed to oligomers present at the AgX surface (molecule enhanced, thus MOSEIRA).This is above those due to amplification (40×, 20 reflections) and enhancement (30×, image dipoles or surface phonon polaritons). In the case of ethanol an excellent initial pentamer spectrum evolves over 8–10 min to a mixture of pentamer, tetramer, and trimer spectra that within another minute forms small oligomers and monomers. We use a new type of cell for infrared spectroscopy containing an AgX planar fiber. The optical configuration leads to a vicinal region at the surface defined by evanescent waves. Within this region are surface‐induced organized species such as ethanol oligomers. The planar AgX fiber supports 20 reflections and transmits light over a wide visible–infrared wavelength range. Short scan times permit the study of volatile substrates or solvents, including the effects of solvent polarity.