As a fast detection method, Fourier transform infrared attenuated total reflection (ATR-FTIR) spectroscopy is seldom used for monitoring soluble sugars in crops. This study aimed to demonstrate the feasibility of leveraging ATR-FTIR coupled with chemometrics to quantify and sort the contents of soluble sugar in tomatoes. Firstly, 192 tomato samples were scanned using ATR-FTIR; subsequently, a quantitative model was developed using PLSR with selected wavelength variables as inputs. Finally, a classification model was estimated through probabilistic neural network (PNN) to determine the samples. The results indicated that ATR-FTIR had successfully captured the spectra from the cellular layers of tomatoes, resulting in a robust PLSR model created by 468 selected variables with a R² value of 0.86, a RMSEP of 0.71%, a ratio of performance to relative percent deviation (RPD) of 1.87, and a ratio of prediction to interquartile range (RPIQ) of 2.1. Meanwhile, the PNN model demonstrated a high rate correct (RC) of 92.17% in identifying whether the samples with a higher soluble sugar content than the limit of detection (LOD at 2.1%). Overall, ATR-FTIR coupled with chemometrics has proven effective for non-destructive determination of soluble sugars in tomatoes, offering new insights into internal monitoring techniques for crop quality assurance.