The present work focuses on synthesis and structural, electronic, and optical properties of pyridinium lead bromides with halogen substituents in the meta position of the pyridine ring. All the compounds have the same spatial symmetry (P21/c) and the same number of formula units (4) in a unit cell. This makes the comparison of their properties straightforward. Both theoretical and experimental studies demonstrate dependence of the bandgap energies on the type of the halogen substituent in pyridinium ring due to an alteration of the crystallographic a-axes. Another effect caused by the type of the halogen substituent on electronic structure of the materials is an alteration of the valence band maxima positions and blue shift of the luminescence excitation maxima originated from contribution of the iodine states into valence band and overlapping of the conduction band states with π* orbitals of organic cations, respectively. A remarkable feature of the synthesized materials is their luminescence observed at room temperature, which demonstrates their potential for optoelectronic applications