Recent interest in two-dimensional (2D) lead-free hybrid organic−inorganic perovskites (HOIPs) has driven significant progress in the development of magnetic and electronic materials. Herein, we systematically compare a series of low-temperature growth of 2D cobalt-based HOIPs (Co-HOIPs) by varying the methylene chain length (n) of n = 1, 2, 3, and 4, for the first time. The Co-HOIP crystal structure with a single carbon chain displays a monoclinic arrangement with a space group of P21/c, while those with two, three, and four methylene chain lengths manifest triclinic crystal structures with a space group of P1. The optical measurements exhibit apparent odd−even effects as a function of the length of the organic ligand. The first-order phase transitions of BA 2 CoCl 4 are distinctly observed at temperatures of 12.46 and 139.77 °C compared to the shorter EA 2 CoCl 4 counterparts. Notably, this particular compound exhibits the highest magnetic saturation and coercive fields with M s = 0.160 emu/g and H c = 19.416 T, respectively. Furthermore, BA 2 CoCl 4 demonstrates superior dielectric properties, as evidenced by the shortest diameter of the equivalent circuit in EIS. These findings underscore the potential of BA 2 CoCl 4 for diverse applications in magnetic and electronic devices, highlighting its promising role in advanced technological applications.