Methyl vinyl ketone (MVK) and crotonaldehyde are chemical isomers; both are also important species in tropospheric chemistry. We report quantitative vapor-phase infrared spectra of crotonaldehyde and MVK vapors over the 540-6500 cm(-1) range. Vibrational assignments of all fundamental modes are made for both molecules on the basis of far- and Mid-infrared vapor-phase spectra, liquid Raman Spectra, along with density functional theory and ab initio MP2 and high energy-accuracy compound theoretical models (WlED). Theoretical results indicate that at room temperature the crotonaldehyde equilibrium mixture is approximately 97% s-trans and Only 3% s-cis conformer. Nearly all observed bands are thus associated with the s-trans conformer, but a few appear to be -uniquely associated with the s-cis conformer, notably nu(c)(16) at 730.90 cm(-1), which displays a substantial intensity increase with temperature (70% upon going from 5 to 50 degrees C). The intensity of the corresponding mode of s-trans conformer decreases with temperature. Under the same conditions; the MVK equilibrium mixture is approximately 69% s-trans conformer and 31% s-cis. W1BD calculations indicate that for MVK this is one of those (rare) cases where there are comparable populations of both conformers, approximately doubling the number of observed bands and exacerbating the vibrational assignments. We uniquely assign the bands associated with both the MVK s-cis conformer as well as those of the s-trans, thus completing the vibrational analyses of both conformers from the same set of experimental spectra. Integrated band intensities are reported for both molecules along with global warming potential values. Using the quantitative IR data, potential bands for atmospheric monitoring are also discussed.