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Abstract Reported is the measurement of infrared absorption spectra of 4‐nitrothiophenol and hydroxyl‐terminated hexa(ethylene glycol) molecules at apices of functionalized atomic force microscope (AFM) probes using resonantly enhanced infrared photoexpansion nanospectroscopy, also known as resonantly enhanced AFM‐IR technique. The experiment demonstrates the applicability of the AFM‐IR technique to perform spectroscopy of only a few tens of molecules on AFM tip apices and demonstrates the potential of the AFM‐IR technique to perform vibrational spectroscopic studies of chemical reactions and molecular conformational changes on the apices of functionalized AFM tips.