Mid-infrared laser excitation of molecules into high-lying vibrational states offers a novel route to realize controlled ground-state chemistry. Here we successfully demonstrate vibrational ladder climbing in the antisymmetric stretch of CO in the condensed phase by using intense down-chirped mid-infrared pulses. Spectrally resolved pump-probe measurements directly observe excited-state absorptions attributed to vibrational populations up to the = 9 state, whose corresponding energy of 2.5 eV is 46% of the dissociation energy. By the use of global fitting analysis, important spectroscopic parameters in the high-lying vibrational states, such as transition frequencies and relaxation times, are quantitatively characterized. Remarkably, our analysis shows that 40% of the molecules are excited above the typical activation barriers in the metal-catalyzed CO conversions. These results not only demonstrate the promising ability of infrared excitation to produce elevated vibrational states but also represent a significant step toward accelerating CO conversions and other chemical processes via mode-specific vibrational excitation.