Keggin-type polyaluminum species (epsilon-Al-13, delta-Al-13, Al-26, Al-30, Al-32) can form upon partial hydrolysis of Al3+-bearing solutions and are important species for water purification and contaminant transport. While the structural features for the major Al3+ polyaluminum species have been delineated, much less is known regarding heteroatom substitution and resultant structures other than the previously identified epsilon-GaAl127+ and epsilon-GeAl128+ cations. Single-atom substitution within polyaluminum species can change the surface reactivity within water treatment scenarios; thus, it is important to understand heteroatom incorporation within this system. The present work describes the synthesis and characterization of two novel Ga3+-substituted Keggin-type polyaluminum species. Na [GaO4Al12(OH)(24)(H2O)(12)] (2,6-NDS)(4)(H2O)(20.5)(delta - GaAl12) and [Ga2O8Al28.5Ga0.5(OH)(58)(H2O)(27)(SO4)(2)](SO4)(4)Cl-7(H2O)(8.5)(Ga2.5Al28.5) were crystallized from a thermally aged, partially hydrolyzed Ga3+/Al3+ solution. Structural refinement from single-crystal X-ray diffraction indicated fully occupied Ga3+ within tetrahedral site(s) of both isolated species. Partial substitution was observed for octahedral sites for the larger Ga2.5Al28.5 cluster. The chemical compositions of both clusters were confirmed by inductively coupled plasma mass spectrometry (ICP-MS). Density functional theory (DFT) calculations corroborated the structural refinement, with the energetics of Ga3+ substitution suggesting preferential substitution within tetrahedral sites for both species. Additional theoretical work suggests that the rotated trimer in delta-GaAl12 is highly reactive, which can serve as the driving force in the formation of the Ga2.5Al28.5 cluster.