In the title compound, fac-[Re(C19H13N3S)(CO)3(H2O)]PF6·CH3OH, the coordination environment of the ReI atom is octahedral with a C3N2O coordination set. In this molecule, the N,N' bidentate ligand, (E)-4- (benzo[d]thiazol-2-yl)-N-(pyridin-2-ylmethylidene)aniline, and the monodentate aqua ligand occupy the three available coordination sites of the [Re(CO)3]+ core, generating a '2 + 1' mixed-ligand complex. In this complex, the Re--C bonds of the carbonyl ligands trans to the coordinating N,N0 atoms of the bidentate ligand are longer than the Re--C bond of the carbonyl group trans to the aqua ligand, in accordance with the intensity of their trans effects. The complex is positively charged with PF6- as the counter-ion. In the structure, the complexes form dimers through π-π intermolecular interactions. O--H···Oand O--H···N hydrogen bonds lead to the formation of stacks parallel to the a axis, which further extend into layers parallel to (011). Through O--H···F hydrogen bonds between the complexes and the PF6- counter-anions, a three-dimensional network is established. [ABSTRACT FROM AUTHOR]