Extensive research has been dedicated to exploring the potential applications of organic-inorganic hybrid metal halides in optoelectronics. This study presents findings on three metal halides based on phenylbutanammonium (PBA). Specifically, (PBA)2MnBr4(H2O)2 and (PBA)2Sn(IV)Cl6 exhibit zero-dimensional structures with P21/c and Pnma space groups, respectively, while (PBA)2Sn(II)Br4 features a two-dimensional structure with P1̅ space group. Under UV excitation, (PBA)2MnBr4(H2O)2 exhibits double emission arising from the 4T1 → 6A1 transitions of Mn2+ in two distinct coordination environments. The emission spectrum of (PBA)2SnCl6 aligns with that of PBACl, suggesting that the luminescence originates from the organic component. The yellow emission of (PBA)2SnBr4 is attributed to the self-trapped excitons. This study introduces the PBA series of compounds, revealing that varying metal ions and halogen combinations can adjust the structural dimensions and influence optical properties. The insights gained from this work serve as a guide for the preparation of efficient white light-emitting diodes.