The metal-organic framework {[Fe(2,2'-bipyridine)(CN)(4)](2)Co-(4,4'-bipyridine)}center dot 4H(2)O (Fe2Co-MOF) with single-chain magnetism undergoes an intermetallic charge transfer that converts the Fe2Co charge/spin configurations from Fe-LS(3+)-Co-HS(2+)-Fe-LS(3+) to Fe-LS(2+)-Co-LS(3+)-Fe-LS(3+) (LS = low spin, HS = high spin) around 220 K under ambient pressure. A series of coherent phase transitions in structure, magnetism, permittivity and ferroelectricity are found to take place accompanying with the charge transfer, making Fe2Co-MOF a unique ferroelectric single-chain magnet at low temperature. Moreover, our detailed measurements of magnetization, dielectric constant, and Raman scattering under high pressures illustrate that the charge transfer as well as the resulting multifunctional transitions can be readily induced to occur at room temperature by applying a tiny external pressure of about 0.5 kbar. The present study thus provides a pressure well-controllable multifunctional material with potential applications in a broad temperature region across room temperature.