The mechanism on ferroelectric phase transitions is mainly attributed to the displacive and/or order-disorder transition of internal components since the discovery of the ferroelectricity in 1920, rather than the breaking and recombination of chemical bonds. Here, we demonstrate how to utilize the chemical bond rearrangement in a diarylethene-based crystal to realize the light-driven mm2F1-type ferroelectric phase transition. Such a photoinduced phase transition is entirely driven by switchable covalent bonds with breaking and reformation, enabling the reversible light-controllable ferroelectric polarization switching, dielectric and nonlinear optical bistability. Moreover, light as quantized energy can achieve contactless, nondestructive, and remote-control operations. This work proposes a new mechanism of ferroelectric phase transition, and highlights the significance of photochromic molecules in designing new ferroelectrics for photocontrol data storage and sensing.