Drivers pay unequal attention to different road environmental elements and visual fields, which greatly influences their driving behavior. However, existing collision warning systems ignore these visual characteristics of drivers, which limits the performance of collision warning systems. Therefore, this study proposes a novel collision warning system based on the visual road environment schema, in order to enhance the support for avoiding potential dangers in objects and areas that are easily overlooked by the drivers’ vision. To capture the above visual characteristics of drivers, the visual road environment schema that consists of the semantic layer, the scene depth layer, the sensitive layer, and the visual field layer is established by using several different deep neural networks, which realizes the recognition, quantization, and analysis of the road environment from the drivers’ visual perspective. The effectiveness of the novel collision warning system is verified by the driving simulation experiment from six indicators, including warning distance, maximum lateral acceleration, maximum longitudinal deceleration, minimum collision time, reaction time, and heart rate. Additionally, a grey target decision-making model is built to comprehensively evaluate the system. The results show that compared with the traditional collision warning system, the novel collision warning system proposed in this study performs significantly better and can discover potential dangers earlier, give timely warnings, enhance the vehicles’ lateral stability and driving comfort, shorten reaction time, and relieve the drivers’ nervousness. By integrating the drivers’ visual characteristics into the collision warning system, this study could help to optimize the existing collision warning system and promote the mutual understanding between intelligent vehicles and human drivers.