The first examples of mixed-anion lanthanide galloborates, namely, Ln(2)Ga[B3O6(OH)](2)[B7O9(OH)(2)](CH3CO2)(2) [Ln = Y (1), Sm (2), Eu (3), Gd (4), Dy (5)], have been obtained through hydrothermal synthesis. The title compounds are isomorphic and belong to monoclinic space group C2/c (No. 15). Their structures possess [B7O13(OH)(2)] borate layers further bridged with [B3O7] dusters to give a three-dimensional (3D) borate framework displaying two types of rhombus-like B14O14 14-membered-ring (14-MR) channels along the b axis. The Ga3+ ions are octahedrally coordinated and located at one end of the B14O14 14-MR channels, forming small tunnels of B7Ga 8-MRs, which are filled by the Ln(III) ions. The Ln ions and Ga cations are further held together by bridging acetate anions. It is worth noting that in these compounds there are two different types of borate dusters and two types of anions that are uncommon in the borates reported. Luminescent studies revealed the characteristic emission bands of Ln ions for compounds 2-5, and the luminescent lifetimes are 3.6, 0.86, and 3.05 ns for compounds 2, 3, and 5, respectively. Magnetic measurements suggest that there are antiferromagnetic interactions between magnetic centers for compounds 2-5.