A niccolite series of bnH22+M(HCOO)32 (bnH22+=1,4‐butyldiammonium) shows four kinds of metal‐dependent phase transitions, from high temperature para‐electric phases to low‐temperature ferro‐, antiferro‐, glass‐like, and para‐electric phases. The conformational flexibility of bnH22+ and the different size, mass, and bonding character of the metal ion lead to various disorder‐order transitions of bnH22+ in the lattice and relevant framework modulations, thus different phase transitions and dielectric responses. The magnetic members display a coexistence or combination of electric and magnetic orderings in the low‐temperature region. Not just a phase! A niccolite series of bnH22+M(HCOO)32 (bnH22+=1,4‐butyldiammonium) displays four types of phase transitions, from the high‐temperature para‐electric phases to low‐temperature ferro‐, antiferro‐, glass‐like, and para‐electric phases, due to the subtle synergy of the conformational flexibility of bnH22+ and the different characters of the metal ions.