Motorways are typically the safest road environment in terms of injury crashes per million vehicle kilometres; however, given the high severity of crashes occurring therein, there is still space for road safety improvements. The objective of this study is to compare the classification performance of five machine learning techniques for predictions of crash risk levels of motorway segments. To that end, data on crash risk levels, driving behaviour metrics, and road geometry characteristics of 668 motorway segments were exploited. The utilized dataset was divided into training and test subsets, with a proportion of 75% and 25%, respectively. The training subset was used to train the models, whereas the test subset was used for the evaluation of their performance. The response variable of the models was the crash risk level of the considered motorway segments, while the predictors were various road design characteristics and naturalistic driving behaviour metrics. The techniques considered were Logistic Regression, Decision Tree, Random Forest, Support Vector Machine, and K-Nearest Neighbours. Among the five techniques, the Random Forest model achieved the best classification performance (overall accuracy: 89.3%, macro-averaged precision: 89.0%, macro-averaged recall: 88.4%, macro-averaged F1 score: 88.6%). Moreover, the Shapley additive explanations were calculated in order to assist with the interpretation of the model’s outcomes. The findings of this study are particularly useful as the Random Forest model could be used as a highly promising proactive road safety tool for identifying potentially hazardous motorway segments.