By using multi-level modeling, this study explores the impact of students' perception of the quality of the teacher-student relationship and family structure on student achievement after controlling for socioeconomic status (SES), school urbanicity, and school control. The data from 750 schools and 17,000 10th grade students were analyzed. Family structure and student's perception of teacher-student relationship, and SES were student-level; school urbanicity and school control were school-level variables. The findings indicated that students, who had a positive perception about their relationship with their teachers, came from families including two biological parents, and had high SES and high math achievement. Students' SES and attending public school in urban areas were found to be significantly related to students' math achievement. The math score for public school students was lower than students from private and Catholic schools. The further research should have a design addressing the impact of these variables in a longitudinal term.