A family of five hybrid ABX(3) perovskites has been synthesized using hypophosphite (H2POO)(-) as the X-site ion. These compounds adopt the general formula [Am]lVin(H2POO)3, where Am = guanidinium (GUA), formamidinium (FA), imidazolium, triazolium, and dabconium. We explore the diverse structural and phase transition behavior of these materials through single crystal diffraction measurements and demonstrate contrasting magnetism in two of the phases, Am = GUA and FA, that arises from structural distortions. The results show that hypophosphite perovskites offer a promising platform for generating new functional materials.