Unattended children and migrated children are unique phenomenon in China. As development of Chinese economy, a lot of farmers come to city and ask for jobs. Some peasant-worker’s children who follow their parents enter into cities become “migrated children”; some peasant-worker’s children who still stay at hometown and were left with their relatives were called “unattended children”. Because living environments of unattended and migrated children are worse than those of ordinary children, problem behavior of unattended children and migrated children attracts much more attention. Previous research discussed separately the situation of problem of unattended children or migrated children, however, few researches focus on the difference of the situation of problem behavior and its effect mechanism between the two groups of children, so this study was used to make up this drawback. To achieve this purpose, a questionnaire was administered to 4279 migrated children, unattended children and ordinary rural children from Beijing, Shanxi and Henan province. First, MANOVA was used to discuss the characteristic of grade and gender of the three groups of children. Second, MANOVA was used to discuss the differences of the social negative environment, parent-child relationships, teacher-student relationship and peer relationship among the three groups of children. At last, the three kinds of personal relationships as moderators were used to examine the moderating effect of social negative environment on problem behavior for the three groups of children by SEM. The findings suggested that (1) mild problem behavior of migrated children from elementary school are worse than those of unattended children and ordinary children; serve problem behavior of migrated and unattended children from elementary school are worse than those of ordinary children; mild problem behavior of migrated children from secondary school are worse than those of unattended children whose mild problem behavior are worse than those of ordinary children; (2) parent-child relationship, teacher-student relationship and social negative environment of unattended children and ordinary children are better than those of migrated children; (3) parent-child relationship and peer relationship can moderate the prediction of social negative environment on problem behavior of migrated and ordinary children; peer relationship can moderate the prediction of social environment on problem behavior of unattended and ordinary children. Finally, the present research discussed the characteristic of problem behavior of unattended and migrated children and the difference of personal relationship and social negative environment among the three groups of children. Importantly, though discussing the mediated effect of social negative environment on problem behavior, the three kinds of personal relationship can be used to decrease the passive effect of social negative environment. Specifically, ordinary children can use parent-child relationship and peer relationship to relieve the passive effect of social negative environment on problem behavior; unattended children can use peer relationship to alleviate the negative effect of social negative environment and parent-child relationship can be used to ease the negative effect by migrated children.