This study explores the remarkable properties of liquescent open-shell ionic molecular systems, emphasizing the magnetic and photophysical characteristics arising from their associated structures in the condensed state under various conditions. Well-investigated open-shell molecules, namely, phenothiazine, dihydrophenazine, and tetrathiafulvalene radical cations, and bis(malononitriledithiolato)nickel(III) anionic complexes were examined, and the concept of liquescent open-shell ionic molecular systems was devised. Transformations in their associated structures are induced by external stimuli, resulting in significant variations in their physical properties. These experimental findings open new avenues for exploring and applying stimuli-responsive molecule-based materials.