This paper seeks to elucidate the relationship between cycle safety and urban road structure regarding connectivity of bicycle network, by comparing the cases of Changwon and Ansan in South Korea. Both cities have significantly different numbers of bicycle accidents but share the same general urban planning idea as the car-oriented industrial cities, and similar bicycle sharing systems implemented in the last decade. Numerous studies on urban cycle safety have been produced over the past decade, but only a limited number of studies have concentrated on cycle safety about urban road structure with real-world accident data. With the awareness of past studies’ limitations, this paper focuses on identifying why cycle safety shows different characteristics in Changwon and Ansan, in particular regarding its linkage to road structure. This research analyzed the relationship between road structure of Changwon and Ansan and their bicycle safety factors that include entire road networks, cycleway networks, and the structure of particular intersection with the location of bicycle accidents by space syntax and spatial analysis tools. The findings suggest that the structures of the bicycle network which has lower connectivity and complicated structure of particular intersections show the lower cycle safety conditions. This research provides insights for further bicycle sharing plans and for creating a safe environment for citizens in other cities, especially contemporary planned cities.