Conformational isomerism plays a central role in organic synthesis and biological processes; however, effective control of isomerization processes still remains challenging and elusive. Here, we propose a novel paradigm for conformational control of isomerization in the condensed phase, in which the polarity of the solvent determines the relative concentration of conformers at the interfacial and bulk regions. By the use of state-of-the-art molecular dynamics simulations of glyoxal in different solvents, we demonstrate that the isomerization process is dipole driven: the solvent favors conformational changes toward conformers having molecular dipoles that better match its polar character. Thus, the solvent polarity modulates the conformational change, stabilizing and selectively segregating in the bulk vs the interface one conformer with respect to the others. The findings in this paper have broader implications affecting systems involving compounds with conformers of different polarity. This work suggests novel mechanisms for tuning the catalytic activity of surfaces in conformationally controlled (photo)chemical reactions and for designing a new class of molecular switches that are active in different solvent environments.