Ferroelectric materials have gained significant interest in various kinds of water splitting, but the study of ferroelectric materials for electrocatalytic water splitting is in its infancy. Ferroelectric materials have spontaneous polarization below their Curie temperature due to dipolar alignment, which results in surface charges. In 2D ferroelectric materials, spontaneous polarization depends on thickness. Herein, we report that thickness-dependent ferroelectric polarization in 2D nanosheets can also accelerate the oxygen evolution reaction (OER) along with the tailored active surface area of exposed crystalline facets, which improves the electrocatalytic activity relatively. Iron-substituted BiOCl nanosheets of varying thickness are fabricated by varying the pH using a facile coprecipitation method. The substituted iron enhances polarization and electrochemical active sites on the surface. The findings in this study show that the exposed (001) facet and higher thickness of the nanosheets have high ferroelectric polarization and, in turn, superior electrocatalytic activity and remarkable stability, requiring low overpotentials (348 mV and 270 mV at 100 mA/cm2 and 10 mA/cm2) in alkaline (1.0 M KOH) electrolyte. As the thickness of the nanosheets is decreased from 140 to 34 nm, the electrocatalytic performance of iron-substituted BiOCl nanosheets starts to reduce due to the lower Coulomb-Coulomb interaction and the increasing depolarization.