A facile synthesis of piperidinium 3,3'-(arylmethylene) bis (2-hydroxynaphthalene-1,4-dione) analogs as organic salts is described by the one-pot pseudo-four-component reaction between 2-hydroxy-1,4-naphthoquinone, aromatic aldehydes, and piperidine. The single-crystal X-ray diffraction analysis of these systems confirms that the stabilized predominant interactions are N-H\... O and O-H\... O hydrogen bonds. Mild and clean reaction conditions, high atom economy, and operational simplicity of this one-pot multicomponent reaction coupled with excellent yields and no need for column chromatography have transformed this procedure to be a superior synthetic route for the efficient formation of families of naphthoquinone-derived compounds.