The intrinsic symmetry breaking in the breathing kagome lattice of layered Nb₃Cl₈ provides a unique mechanism for realizing electrically polar surfaces. In each monolayer, the trimerization of Nb atoms breaks inversion and mirror symmetries, generating an out-of-plane electric dipole. The AB-stacked α phase arranges adjacent layer dipoles antiferroelectrically, leaving the uncompensated surface polarization strictly governed by layer parity. Here, using atomic force microscopy operated in Kelvin probe force microscopy mode, we directly visualize layer-dependent polarization states in exfoliated Nb₃Cl₈ flakes and resolve a pronounced odd-even oscillation of the surface electrostatic potential. Beyond this parity-locked antiferroelectric order, we further identify intralayer polar domains in which local atomic reconstructions of the breathing kagome network reverse the out-of-plane dipole of the surface layer, producing ferroelectric-like stacking configurations. By interfacing monolayer MoSe₂ with Nb₃Cl₈, we demonstrate that these surface-polarization textures effectively modulate adjacent excitonic emission through domain-dependent interfacial band alignment and charge transfer. Our findings establish Nb₃Cl₈ as an intrinsic layer-polarized van der Waals platform and show that layer parity provides powerful structural degree of freedom for programming excitonic and optoelectronic responses at van der Waals interfaces.