This paper investigates road safety levels and geometric design consistency in a road network in Greece concerning road alignment characteristics. Published literature has proved that road accidents and road safety, in general, are directly connected to the road network’s geometrical design. Hence, there has been an attempt to select the optimum road design using modern computational systems in recent years. The present research aims to evaluate the risk level of the existing road network, identifying the road sections and road curves with a reduced provided level of road safety and, therefore, with an increased possibility for road accidents, and correlate the results between two widely used software. This research examines two discrete methodologies today for evaluating the provided road safety level based on a road network case study on Chios in Eastern Greece. The two methodologies present similar results, highlighting their advantages and disadvantages, and have a statistically significant correlation according to the level of road safety achieved. The research concludes that the correlation is proportionally higher in road segments with larger curve radii. A further research expansion topic could be the insertion of the number or severity of accidents in the analysis to get a holistic notion of the road safety condition.