Reactions as the attack by naphthenic and hydrogen sulfide have caused corrosion problems in the petroleum industry due to they affect the crude oil heating furnaces and distillation towers at temperatures between 220 and 400 °C. The total acid number (TAN) measurement has been used as a test to quantify the acid compounds in crude oils and has shown to be a reliable indicator of their corrosion degree. However, the standard method for the TAN measurement, ASTM D-644, involves long times, environment unfriendly wastes and high costs for each analysis. A more appropriate method for the TAN determination is implemented in this paper, by correlating Fourier transform infrared spectroscopy (FTIR) spectral data of the samples with the standard method measurements using multivariate regression models. In particular, the intensities and frequencies of their mid-infrared attenuated total reflectance (MIR-ATR) spectra (4000 - 400 cm-1) are used as independent variables of several principal component regression (PCR) and partial least squares regression (PLSR) models. The latter are employed to correlate the spectra with their respective TAN values so as to obtain a suitable prediction model. Twenty-six (26) samples of Colombian crude oils are used for the study with a TAN ranging from 0.1 to 6.8 mg KOH/g crude oil (ASTM D-664). The models are evaluated according to the coefficient of determination (R2), the root mean square error of calibration (RMSEC) and of prediction (RMSEP). The best model is obtained via PLSR using as few as four components (i.e. factors), which attains a calibration R2 of 0.981 and an RMSEC of 0.317 mg KOH/g crude oil, while for prediction it attains an R2 of 0.996 and an RMSEP of 0.160 mg KOH/g crude oil. It is observed that the functional groups COOH, CH3 and CH2 contribute the most to the prediction models. The designed methodology is faster and environmentally friendly since it does not require sample pretreatment and the use of toxic reagents, and of low-cost compared with the standard procedure since FTIR measurements can be easily taken anywhere using a hand-held or portable spectrometer and a laptop.