We report a solvent-free mechanochemical route for the selectively synthesis of three different caesium cobalt chlorides: CsCoCl3, Cs2CoCl4, and Cs3CoCl5, by simply tuning the CsCl : CoCl2 precursor ratio. This is the first comprehensive comparative study of these phases synthesized in pure form, enabling a clear correlation between composition, crystal structure, and optoelectronic properties. Each phase exhibits a unique Co2+ coordination geometry: octahedral in CsCoCl3 and tetrahedral in Cs2CoCl4 and Cs3CoCl5, as revealed by XRD, SEM-EDS, Raman, and XPS, with several features reported here for the first time. All phases display high thermal stability and narrow optical bandgaps (1.65-1.70 eV), supported by ligand field analysis and CIE colorimetry. Valence and conduction band energies determined by VB-XPS and cyclic voltammetry reveal a systematic, composition-driven tuning of energy levels across the series. Importantly, the band edge alignment are suitable for visible-light-driven hydrogen evolution and photovoltaic applications. SCAPS-1D simulations predict power conversion efficiencies up to 17.1%, positioning these halocobaltates as promising absorbers. Altogether, this work introduces a scalable synthesis route and demonstrates the potential of cobalt-based halide frameworks as modular systems for solar energy conversion and photocatalysis.