The search for new high-performance hybrid metal halide phases with exotic structure types and unique functionalities has emerged recently. With the wide selection pool of metal, halide and organic component choices, targeted syntheses and rational design strategies can expedite the advancement and understanding of these materials. We have been working on a series of new metal halide families gearing towards different properties such as photoluminescence, circularly polarized luminescence and second harmonic generation. Highly luminescent systems combine emissive metal centers Mn, Cu or Sb and bulky rigid organic cations/ligands. Another strategy of controlling the symmetry is through the directional coordination via organic cationic ligands, where asymmetry arises with the complexity of bimetallic halides and cationic ligands. Neutral solvent ligands are used to trap hydroscopic rare earth metals and incorporate them into the bimetallic low-dimensional systems with group V metals. We have successfully demonstrated several new metal halide material systems with tunable and superior optoelectronic properties.