The accuracy inherent in the measurement of interproton distances in small molecules by nuclear Overhauser enhancement (NOE) and rotational Overhauser enhancement (ROE) methods is investigated with the rigid model compound strychnine. The results suggest that interproton distances can be established with a remarkable level of accuracy, within a few percent of their true values, using a straight-forward data analysis method if experiments are conducted under conditions that support the initial rate approximation. Dealing with deviations from these conditions and other practical issues regarding these measurements are discussed.