Thirty-five representative and suitably selected roasted coffee samples were characterised by near-infrared (NIR) spectroscopy and used to prepare the corresponding espresso samples to be subsequently subjected to sensory evaluation by trained panellists. The main purpose was to investigate the relationships between certain crucial sensory attributes of espresso coffees, including perceived acidity, mouthfeel, bitterness and aftertaste, and near-infrared spectra of original roasted coffee samples, in such a way that non-destructive near-infrared reflectance measurements would be used to predict all these sensory properties with a decisive influence from a quality assurance standpoint. Separate calibration models based on partial least squares regression (PLS), correlating NIR spectral data of roasted coffee samples with each sensory attribute of espresso samples studied, were developed. Wavelength selection was also performed applying iterative predictor weighting–PLS (IPW–PLS) in order to take into account only significant and characteristic spectral features, in an attempt to improve the quality of the final regression models constructed. Using IPW–PLS regression, prediction of the four sensory responses modelled was performed with high accuracy, with root mean square errors of the residuals in cross-validation (RMSECV) ranging from 4.7 to 7.0%. Thus, the results provided by the high-quality calibration models proposed in the present study, comparable in terms of accuracy to the evaluations provided by a trained sensory panel, are promising and prove the feasibility of using a similar methodology in on-line or routine applications to predict the sensory quality of unknown espresso coffee samples via their respective NIR roasted coffee spectra.