Diabetic sensorimotor polyneuropathy (DSPN) is a major complication in patients with diabetes mellitus (DM), and early detection or prediction of DSPN is important for preventing or managing neuropathic pain and foot ulcer. Our aim is to delineate whether machine learning techniques are more useful than traditional statistical methods for predicting DSPN in DM patients. Four hundred seventy DM patients were classified into four groups (normal, possible, probable, and confirmed) based on clinical and electrophysiological findings of suspected DSPN. Three ML methods, XGBoost (XGB), support vector machine (SVM), and random forest (RF), and their combinations were used for analysis. RF showed the best area under the receiver operator characteristic curve (AUC, 0.8250) for differentiating between two categories—criteria by clinical findings (normal, possible, and probable groups) and those by electrophysiological findings (confirmed group)—and the result was superior to that of linear regression analysis (AUC = 0.6620). Average values of serum glucose, International Federation of Clinical Chemistry (IFCC), HbA1c, and albumin levels were identified as the four most important predictors of DSPN. In conclusion, machine learning techniques, especially RF, can predict DSPN in DM patients effectively, and electrophysiological analysis is important for identifying DSPN.