Three novel bismuth(III) complexes of the formulae [Bi(3-apac)2(H2O)Cl3](3-apac)2 (1), [Bi(μ-pda)(H2O)Cl]n (2) and [Bi(6,6′-bpdc)(H2O)(μ-Cl)] (3) (where 3-apac = 3-aminopyrazine-2-carboxylic acid, H2pda = pyridine-2,6-dicarboxylic acid, 6,6′-H2bpdc = 2,2′-bipyridine-6,6′-dicarboxylic acid) were synthesized. The X-ray crystallographic investigation reveals that 1 is a mononuclear compound and offers the first example of Bi(III) complex which proton transfer occurs in ligand molecules. 2 is a dinuclear coordination polymer, which consists of two [Bi(μ-pda)(H2O)Cl] units via two bridging O atoms of two pda2− ions. And the dinuclear complex 3 is built up from two Bi3+ ion cores which are bridged through two Cl– ions. Furthermore, the photocatalytic activity of 1–3 toward the degradation of Rhodamine B (RhB) was explored, and the mechanism of the photocatalytic degradation was discussed. The results indicate that 2 and 3 are good candidates for the photocatalytic degradation of RhB.