Scientific evaluation of pear maturity is important for commercial reasons. Near-infrared spectroscopy is a non-destructive method that could be used for rapid assessment of pear maturity. The aim of this study was to develop a reasonable and effective method for the assessment of Starkrimson pear maturity using near-infrared technology. Partial least squares regression and five classification methods were used for analysis of the data. Among the indices used with the competitive adaptive reweighting–partial least squares regression method for quantitation, the visual ripeness index had the best modeling effect (Rp2: 0.87; root mean square error of prediction: 0.39). The classification model constructed with the visual ripeness index and post-ripeness score gave a cross-validation neural network model with the best classification effect and the highest accuracy (classification accuracy: 88.7%). The results showed that combination of quality indices with near-infrared spectroscopy was effective for rapidly evaluating the maturity of Starkrimson pears.