Several ditopic ligands containing two tridentate bishydrazone coordination subunits and their Zn(II) and Cd(II) [2 × 2] grid-type complexes were prepared and their photoluminescent properties studied. A special attention was devoted to the influence of the orientation of the hydrazone group NNin the core of the ligands and their complexes. Its reversal from [pyridineNNpyrimidine] (L1) to [pyridineNNpyrimidine] (L2) has a strong impact on the observed absorption and emission behaviour of particular ligands (L1 and L2) as well as of their [2 × 2] grid assemblies. The further lateral functionalization of the ligands led to different emission quantum yields of the resulting grids, while their emission and absorption spectra varied very little. The simplest derivative L1 turned out to have the best performance with, for its Zn(II) complex, relatively high quantum yield 60%.