Drivers’ non-compliance with rules is a prominent factor in collisions with trains at railway level crossings. Road user impatience and frustration has been identified as an underlying factor in non-compliance and can be characterised as a specific risk factor. However, research on non-compliance related to waiting times and driver inconvenience lacks in the literature. This paper, therefore, seeks to enhance the currently limited understanding of the relationship between waiting times and risky driver behaviour. An Advanced Driving Simulator was used to obtain objective measures of level crossing non-compliance. Subjective measures on driver frustration and decision-making processes were also collected. Sixty participants completed six driving tasks each, with the tasks varying in terms of traffic conditions, number of trains and associated waiting times. This study shows that increased waiting times result in higher levels of frustration and an increased likelihood of risky driving behaviour, particularly for waiting times longer than three minutes. Non-compliance included entering the activated crossing before boom gates are down, entering the crossing after the train passage but before signals are deactivated, stopping/reversing on the crossing. Subjective data revealed that participants did not comply with level crossing rules due to factors including time pressure, impatience/frustration and low perceived risk. The results suggest that, where possible, waiting times should be standardised at values lower than three minutes to reduce the likelihood of risky road user behaviour.