Solvothermal reactions of 4-(pyrid-4'-yl)-3,5-dimethylpyrazole (HPpz) with CuBr in two mixed solvents, NH3 center dot H2O/EtOH and NH3 center dot H2O/MeCN, afforded respectively a copper(I) trimer, [Cu(Ppz)](3) (1), and a polymer, {[Cu(Ppz)](3)[CuCN](3)} (2), both containing the [Cu(Ppz)](3) entity as a building block. The products were found to be photoluminescent and, more interestingly, when cooled from room temperature to 10 K, they showed a blue shift followed by a red shift, (hereafter shortened to a red-after-blue shift) of emission.