Roof falls in coal mine roadways are the main causes of many casualties, shutdowns and production plan delays. To understand the relationship between the influencing factors of roadway roof fall accidents and the importance ranking of the accidents, we will reduce safety accidents in coal mines. To enable the timely prediction and control of roadway roof fall risks, based on the investigation of many roadway roof fall risk factors, 12 evaluation indexes such as the roadway roof rock thickness, geological conditions and roadway section shape were selected. An evaluation index system of roadway roof fall risks is constructed. A risk degree standard of roadway roof falls is proposed. The risk evaluation model of roadway roof falls was established by using the combination weight of the analytic hierarchy process (AHP), entropy weight method (EW) and matter element extension theory. According to the principle of the maximum membership degree, the risk degree of roadway roof falls is determined. Based on Java Web, a risk assessment system for roadway roof falls was developed. We name the system Multiple Weight-Material Element Web (MW-MEW). The MW-MEW system was used to evaluate the risk degree of roof falls in the C9 return airway of the Xingu Coal Mine. Compared with the evaluation results of the AHP matter element extension model, it is found that the evaluation results of the MW-MEW system are more in line with the actual engineering conditions. The successful application of the MW-MEW system will provide new avenues for the quantitative evaluation of roof fall risks in coal mine roadways.