We propose the concept of local acidity in condensed-phase chemistry in this work. The feature is demonstrated in trifluoroethanol (TFE) by employing two Fourier-transform infrared spectroscopy (FTIR) nitrile probes, acetonitrile (CH3CN) and benzonitrile (PhCN). Specifically, three positive excess peaks were found in the binary systems composed of TFE and a probe using excess spectroscopy. To characterize the local acidity quantitatively, we have tried to correlate the wavenumbers of the positive excess peaks of the probes and the pKa values in water of a series of XH-containing compounds (X = O, N, and C). Good linear relationships were discovered. Accordingly, three different pKa values of TFE were determined based on the three positive excess infrared peaks, which are attributed to the monomer, dimer, and trimer of TFE with the help of quantum-chemical calculations. The concept of local acidity and its quantitative evaluation enrich our knowledge of acid-base chemistry and will shed light on a better understanding of microstructures of solutions.