The distribution of Al (j) and the structural units distribution of Q~i _T in calcium aluminosilicate melts were studied by means of molecular dynamics simulation. The results show that provided there exists lower-field strength cation relative to Al~(3+), such as alkaline and alkaline earth metals, Al will be four-coordinated but not six-coordinated. Meanwhile, if there exist a large number of higher-field strength cations such as Si~(4+) and little lower-field strength cation, six-coordinated aluminum will be formed. The relation of structural units distribution of Q~i _T with chemical composition shift was also extracted, showing that as Ca~(2+) exists, the distributions of Q~i _(Si), Q~i _(Al) or Q~i _(T) have the similar changing trend with the variation of component. Because of high-temperature effect, the Al-tetrahedral units in melts are greatly active and unstable and there exist dynamic transforming equilibria of Al(3)Al(4) and (Al(5))Al(4). The three-coordinated oxygen and charge-compensated bridging oxygen are proposed to explain phenomena of the negative charge redundancy of AlO_4 and location of network modifier with charge-compensated function in aluminosilicate melts. The distribution of Al (j) and the structural units distribution of Q ~ i _T in calcium aluminosilicate melts were studied by means of molecular dynamics simulation. The results show that provided there lower-field strength cation relative to Al ~ (3+) , such as alkaline and alkaline earth metals, Al will be four-coordinated but not six-coordinated. Meanwhile, there exists a large number of higher-field strength cations such as Si ~ (4+) and little lower-field strength cation The relation of structural units distribution of Q ~ i _T with chemical composition shift was also extracted, showing that as Ca ~ (2+) exists, the distributions of Q ~ i _ (Si), Because of the high-temperature effect, the Al-tetrahedral units in melts are greatly active and unstable and there exists dynamic transforming. Q ~ i _ (Al) or Q ~ i _ (T) equilibria of Al (3) Al (4) and (Al (5)) Al (4). The three- coordinated oxygen and charge-compensated bridging oxygen are proposed to explain phenomena of the negative charge redundancy of alO_4 and location of network modifier with charge-compensated function in aluminosilicate melts.