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The article analyzes switching of intramolecular charge transfer in cruciforms with respect to metal ion sensing. In most, but not all, chromophores, HOMO and LUMO are spatially superimposed. However, adding donor and/or acceptor substituents to cross-shaped chromophores at suitable positions can lead to independent electronic shifts in HOMO and LUMO into opposite directions. In the cruciforms 2-4, the HOMO is located on the distyrylbenzene branch, while the LUMO is situated on the bisarylethynyl axis of the molecule. As a consequence, the intramolecular charge-transfer emission and absorption of such cruciforms is dependent upon solvent polarity. It demonstrates dramatic blue and/or red shifts of emission and absorption upon coordination of metal cations to cruciforms.