Controlling molecular chirality by external stimuli is of great significance in both fundamental research and technological applications. Herein, we report a high-temperature (384 K) molecular ferroelectric of a Cu(II) complex whose spontaneous polarization can be switched associated with flipping of molecular chirality. In this two-dimensional perovskite structure, the inorganic layer is separated by (NH₃(CH₂)₂SS(CH₂)₂NH₃)²⁺ organic cations skewed in a chiral conformation (P- or M-helicityin an individual crystal). As the stereodynamic disulfide bridgedetermines the molecular dipole moment along the polar axis, the chiral organic cation can be converted to its enantiomer as aconsequence of an electric field-induced shift of the S−S moiety relative to its screw axis during the ferroelectric switching. The variation of the molecular chirality is examined with single-crystal X-ray diffraction and circular dichroism spectra. The simultaneous switching of molecular chirality and spontaneous polarization in this perovskite ferroelectric may lead to novel chiral electronic phenomena.