Appropriate spatial distribution of primary and secondary schools for relocated children of migrant workers (RCMW) is extremely valuable to ensure the fair education of special groups and improve the quality of their education. This study used concentration analysis, kernel density estimation (KDE), and coefficient of variation (CV) to measure the spatial agglomeration of these children and their primary and secondary schools in the districts and counties of Liaoning Province from 2008 to 2017 based on government surveys. The results showed that the number of RCMW children in primary and secondary schools increased during the research period and the growth rate of children in primary schools was higher than that of children in junior high schools. The number of primary and secondary schools has changed very little, while the number of secondary schools has dropped sharply. The spatial distribution of RCMW and that of their primary and secondary schools were characterized by a “dual-core” distribution and a three-level (county, city, and provincial capital) gradient aggregation. In addition, kernel density evolved from a balanced distribution to polar nucleus-shaped, clustered, and discretized distributions, respectively. Specifically, the “large” and “super-large” schools were mainly concentrated in cities, showing a clustered pattern. “Medium-sized” and “small” schools were mainly distributed in counties, presenting a discretized pattern. In addition, when the CV of the number of RCMW increased, the imbalanced distribution of schools became more significant. Furthermore, the spatial differentiation of primary and secondary schools for RCMW appeared to be affected by economic development, population size, and related policies in the region.