Abstract The determination of crystal size of chert samples can provide suitable information about the raw material used for the manufacture of archeological items. X-ray diffraction (XRD) has been widely used for this purpose in several scientific areas. However, the historical value of archeological pieces makes this procedure sometimes unfeasible and thus, non-invasive new analytical approaches are required. In this sense, a new method was developed relating the crystal size obtained by means of XRD and infrared spectroscopy (IR) using partial least squares regression. The IR spectra collected from a large amount of different geological chert samples of archeological use were pre-processed following different treatments (i.e., derivatization or sample-wise normalization) to obtain the best regression model. The full cross-validation was satisfactorily validated using real samples and the experimental root mean standard error of precision value was 165Å whereas the average precision of the estimated size value was 3%. The features of infrared bands were also evaluated in order to know the background of the prediction ability. In the studied case, the variance in the model was associated to the differences in the characteristic stretching and bending infrared bands of SiO2. Based on this fact, it would be feasible to estimate the crystal size if it is built beforehand a chemometric model relating the size measured by standard methods and the IR spectra.