A series of four spiropyrans bearing different substituents on the indolic nitrogen were synthesized and their capability of binding mono and bivalent transition metal cations in solution was assessed viaUV-visible absorption spectroscopy. All the compounds responded selectively to the presence of Cu(II) ions producing intense absorption bands in the visible region of their spectra. Bidimensional 1H-NMR and MALDI-TOF MS spectroscopies revealed the formation of SP dimers mediated by Cu(II). This is the first example of cross-coupling mediated by copper(II) in mild conditions causing the symmetric dimerization of spiropyran dyes.