Influence of total aluminum concentration (CAlT) on the generation and transformation of nanosized Al-13 and Al-30 in hydrolytic polyaluminum aqueous solutions was investigated using high field Al-27 NMR and time-developed Al-Ferron complex colorimetry. When prepared at the optimal basicity (B) of Al-13 generation and 80 degrees C, the Al-13 species in polyaluminum solution tends to further polymerize and convert to Al-30 and higher polymers when CAlT > 0.2 mol(.)L(-1), but Al-13 does not convert to Al-30 quantificationally, as the formation of Al-u from Al-13 and Al-30 is accelerated in the same way. The conversion rate of Al-13 is accelerated by the increase in CAlT. When CAlT > 0.75 mol(.)L(-1), Al-13 content decreases rapidly, and Al-30 content increases continuously and becomes the dominant nanometer polynuclear aluminum species. Al-m is one of prerequisites of Al-13 conversion to Al-30. When CAlT increases and B reduces, the polymerization rate between Al-13 and Al-m increases, and at the same time, the dissociation reaction rate of Al-13 and Al-30 by H+ also increases. The latter becomes the dominant reaction in polyaluminum solution with low B value, so Al-30 decreases with the increasing CAlT. The hydrolytic polyaluminum solution with Al-13 content beyond 80% can only be prepared under the condition of CAlT < 0.5 mol(.)L(-1) and optimal B value.