In this work we report fabrication of high-quality AB- and BA-type heterostructured thin films of cubic Cu(II) (A-type) and tetragonal Cu(I) (B-type) coordination polymers (CPs) on the functionalized Au substrate by the layer-by-layer method. Successful growth of Cu(I)-CP on top of Cu(II)-CP was assigned to be due to the interfacial reduction reaction (IRR). Notably, electrical transport measurements across AB- and BA-type heterostructured thin films revealed rectification of current in opposite directions. We have attributed such an interestingly new observation to the formation of a well-defined interface of Cu(II)-CP and Cu(I)-CP resembling a p-n junction-a hitherto unreported phenomenon that is anticipated to open enormous opportunities for the heterostructured thin films of CPs, likewise celebrated interfaces of oxide heterostructures.