Herein, we report a novel layered lead bromide, (CH₃CH[Formula: see text]N[Formula: see text]Br[Formula: see text](CH[Formula: see text]NH[Formula: see text]PbBr₃, where bulky organic cations, (CH₃CH[Formula: see text]N[Formula: see text]Br[Formula: see text](CH[Formula: see text]NH[Formula: see text], amino-ethyl triethyl ammonium [aetriea] were not only incorporated between the inorganic layers but also sandwiched within the inorganic [PbBr₆][Formula: see text] octahedral layered structure. The UV-Visible, photoluminescence spectroscopy (PL), X-ray diffraction (XRD) and a field-emission scanning electron microscope (FE-SEM) result show that the new perovskitoid has a microrod shape with an estimated bandgap of [Formula: see text]3.05 eV. The structural and optoelectronic properties of the [aetriea]PbBr₃perovskitoid were further corroborated by first-principles density functional theory (DFT) calculations. Thermogravimetric analysis (TGA) data show good stability of the [aetriea]PbBr₃perovskitoid. Time-resolved photoluminescence (TRPL) decays from new [aetriea]PbBr₃perovskitoid showing 6 ns average lifetime. These results suggest that doubly charged cation hybrid perovskite materials are potential candidates for optoelectronic applications.