The molecular structure and the expression levels of starch biosynthesis-related genes of three types of high-amylose maize (HAM) genotypes and one normal maize (NM) genotype at 5-35 days after pollination (DAP) were studied. Size exclusion chromatography (SEC) analysis showed that the molecular size of amylopectin molecules in NM increased from 5 to 35 DAP and the amylose content in HAM genotypes increased from 15 to 35 DAP. Correlation analysis for both NM and HAMs combined showed that SBEIIb and ISAII were negatively correlated with the contents of amylose and long amylopectin chains (DP > 30) and positively correlated with the content of short amylopectin chains (DP ≤ 31) and the molecular size of amylopectin molecules. Correlation analysis for only the HAMs showed that amylose content was negatively correlated with SBEI and SSIIa. In both correlation analyses, SSIIa showed a negative correlation with the average chain lengths of amylose chains.