Reactions of [Cu(kinal)2(MeOH)]·MeOH with piperidine in different reaction systems were monitored. The products were identified by means of infrared spectroscopy and X-ray powder diffraction. At 4 °C, two products crystallized. Their compositions were [Cu(kinal)2(Pipe)2] and [Cu(kinal)2(Pipe)2]·2MeCN. The reaction mixture containing acetonitrile changes colour at ambient conditions. Its colour changed from blue-green to brown-red. Similar colour change was detected in a system with propionitrile, whereas a system with benzonitrile in the same reaction time retained the initial colour. This colour change most likely suggests reduction of copper(II) and that apart from a substitution of methanol with piperidine other, more complicated reactions are taking place in the reaction mixture.