Due to environmental stability issues and the presence of lead in high-performing 3D perovskites and organic 2D perovskites have emerged as excellent light-harvesting materials and gained immense attention for optoelectronic applications such as perovskite solar cells (PSCs) as a capping layer as well as a light-harvesting material. In this paper, we have investigated the effect of varying the type of aromatic amines (benzylamines) and alkyl chain length (hexadecyl and tetradecyl substituted benzylamines), incorporated into organic halide 2D perovskites, on their optoelectronic properties. We synthesized the 2D perovskites were synthesized by adopting the ligand assisted reprecipitation (LARP) technique and analysed their optical properties by using the UV–Visible and Photoluminescence, structural composition using thin-film XRD and morphology analysis using scanning and transmission electron microscopy (SEM and TEM). Our experimental finding suggests the formation of various shapes such as quantum dots, cubic shapes and nanorods which depend on the length of the carbon chain attached to the benzylamines.