Spectroscopic analysis was employed to evaluate the quality of three bell pepper varieties within the 350–1150 nm wavelength range. Quality parameters such as firmness, pH, soluble solids content, titratable acids, vitamin C, total phenols, and anthocyanins were measured. To enhance data reliability, principal component analysis (PCA) was used to identify and remove outliers. Raw spectral data were initially modeled using partial least squares regression (PLSR). To optimize wavelength selection, support vector machines (SVMs) were combined with genetic algorithms (GAs), particle swarm optimization (PSO), ant colony optimization (ACO), and imperial competitive algorithm (ICA). The most effective wavelength selection method was subsequently used for further analysis. Three modeling techniques—PLSR, multiple linear regression (MLR), and artificial neural networks (ANNs)—were applied to the selected wavelengths. PLSR analysis of raw data yielded a maximum R2 value of 0.98 for red pepper pH, while the lowest R2 (0.58) was observed for total phenols in yellow peppers. SVM-PSO was determined to be the optimal wavelength selection algorithm based on ratio of performance to deviation (RPD), root mean square error (RMSE), and correlation values. An average of 15 effective wavelengths were identified using this combined approach. Model performance was evaluated using root mean square error of cross-validation and coefficient of determination (R2). ANN consistently outperformed MLR and PLSR in predicting firmness, pH, soluble solids content, titratable acids, vitamin C, total phenols, and anthocyanins for all three varieties. R2 values for the ANN model ranged from 0.94 to 1.00, demonstrating its superior predictive capability. Based on these results, ANN is recommended as the most suitable method for evaluating the quality parameters of bell peppers using spectroscopic data.