The optical properties of the (CnH2n+1NH3)2PbBr4 and (CnH2n+1NH3)2PbI4 samples have been investigated by UV-Vis absorption and photoluminescence spectroscopies at RT. Figures and report the UV-Vis spectra of the two series, while the Tauc plots, used to extract the bandgap values, are reported in Table . The spectra are characterized by narrow absorption peaks on top of the band edge, consistent with stable excitonic population, typical of quantum confinement effect. In both cases a general blue shift is observed by increasing the chain length of the organic cation. The bandgaps (Table ) show small variation along with the increase of the chain lengths except for the two jumps from n=12 to 14 for (CnH2n+1NH3)2PbI4 and from n=8 to 10 for (CnH2n+1NH3)2PbBr4. The corresponding PL spectra are shown in Figures and. The PL spectra well reflect the absorption features, as they show a structured emission involving two main contributions. The structuring of the 2D MHPs emission in 2 main contributions (S1 and S2) has been debated and, with fluence and temperature experiments, most likely attributed to phonon replica of the main line. Additionally, in our samples, this band structuring is more evident for the specimens embedding small alkyl chains. As we introduce longer chains, we also observe an abrupt blues shift of the emissions, of about 120 meV for the main peak passing from n=10 to n=12 in iodide samples, and of about 60 meV moving from n=8 to n=10 in bromide samples (consistent with absorption measurements). The shift is therefore more pronounced in iodide-based samples (see values of the emission peak maximum in Table ).