The safe and efficient operation of highways minimizes the environmental impact, reduces accidents, and promotes the reliability of the transportation infrastructure, all in support of sustainable transportation. The horizontal alignment of highways holds particular importance as it directly impacts driver behavior, vehicle stability, and overall road safety. In many cases, highway inventory data held by infrastructure operators may contain inaccurate or outdated information. The accuracy of the variables used in crash prediction models eliminates possible bias in the variable estimators. This research proposes a methodology to obtain accurate horizontal geometric features from digital imagery based on the analysis of the planimetry, feature geolocation and centerline azimuth sequence. The reliability of the method is verified by means of numerical and statistical procedures. This methodology is applied to 150 km of motorway segments in Portugal. Although it is found that the geometric characteristics of most of the inventory segments closely matched the extracted alignments, very significant differences are found in some sections. The results of the proposed procedure are illustrated with several examples. Finally, the propagation of error in the determination of the geometric design independent variables in the fitting of the statistical models is discussed based on the results.