Coordination polymer (CP) formation is an unexplored area in weak-interaction chemistry due to the difficulty of monitoring the coordination process. By using cold-spray ionization mass spectrometry (CSI-MS), several kinds of coordination compounds were detected when CuI metal and the 4,7-phenanthroline organic bridged ligand were mixed in solution. The observed ion peaks could be reasonably and simply assigned to various combinations of the metal and the ligand without any fragmentation.