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Photofragment spectroscopy is used to measure the vibrational spectra of V2(+)(CH4)n (n = 1–4), V3(+)(CH4)n (n = 1–3), and Vx(+)(CH4) (x = 4–8) in the C–H stretching region (2550–3100 cm−1). Spectra are measured by monitoring loss of CH4. The experimental spectra are compared to simulations at the B3LYP+D3/6-311++G(3df,3pd) level of theory to identify the geometry of the ions. Multi-reference configuration interaction with Davidson correction (MRCI+Q) calculations are also carried out on V2(+) and V3(+). The methane binding orientation in V2(+)(CH4)n (n = 1–4) evolves from η3 to η2 as more methane molecules are added. The IR spectra of metal-methane clusters can give information on the structure of metal clusters that may otherwise be hard to obtain from isolated clusters. For example, the V3(+)(CH4)n (n = 1–3) experimental spectra show an additional peak as the second and third methane molecules are added to V3(+), which indicates that the metal atoms are not equivalent. The Vx(+)(CH4) show a larger red shift in the symmetric C–H stretch for larger clusters with x = 5–8 than for the small clusters with x = 2, 3, indicating increased covalency in the interaction of larger vanadium clusters with methane.