It is well known that human errors is involved in most of maritime accidents. For the purpose of reducing the influence of human elements on maritime activities, it is necessary to identify the human unsafe acts in those activities The commonly used methods in identification of human unsafe acts are maritime accident statistics or case analysis. With the statistics data, people could roughly identify what kinds of unsafe acts or human errors have played active role in the accident, however, they often neglected some active unsafe acts while overestimated some mini-unsafe acts because of the inherent shortcoming of the methods. There should be some more accurate approaches for human error identification in maritime accidents. In this paper, the application of technique called grey relational analysis (GRA) into the identification of human unsafe acts is presented. GRA is used to examine the extent of connections between two digits by applying the methodology of departing and scattering measurement to actual distance measurement. Based on the statistics data of maritime accidents occurred in Chinese waters in last 10years, the relationship between the happening times of maritime accidents and that of unsafe acts are established with GRA. In accordance with the value of grey relational grade, the identified main human unsafe acts involved in maritime accidents are ranked in following orders: improper lookout, improper use of radar and equivalent equipment, error of judgment, act not in time, improper communication, improper shiphandling, use of unsafe speed, violating the rule and ignorance of good seamanship. The result shows that GRA is an effective and practical technique in improving the accuracy of human unsafe acts identification.