The nature and location of copper in Cu/SSZ‐13 zeolites synthesized by using a one‐pot hydrothermal approach with Cu–tetraethylenepentamine as a template and by the ion exchange of SSZ‐13 were investigated by applying H2‐temperature‐programmed reduction, FTIR, EPR, and in situ Raman spectroscopic techniques. The one‐pot synthesized Cu/SSZ‐13 zeolite contains predominantly isolated copper ions in the large cages, whereas copper species in the ion‐exchanged Cu/SSZ‐13 zeolite occupy sites in the large cages of the chabazite (CHA) structure and the six‐membered rings of the CHA structure. If the one‐pot synthesized Cu/SSZ‐13 zeolite is exchanged with the NH4NO3 solution in addition to the removal of a part of copper ions, the remaining copper ions in the CHA structure relocated from the large cages to the six‐membered rings. Isolated copper dominated in all Cu/SSZ‐13 zeolites. The in situ Raman spectra demonstrated that CuOCu dimers form at higher copper content. The bis‐μ‐oxo dicopper(III) complex is observed only in the ion‐exchanged sample upon dehydration. The higher NO selective catalytic reduction activity of the one‐pot synthesized sample in a wide temperature range appears to be due to the predominance of isolated Cu2+ sites in the large cages, and their higher reactivity is possibly owing to the lower stability of Cu2+ at these sites. Copper in uniform: Temperature‐programmed reduction of hydrogen and Raman spectroscopy of Cu/SSZ‐13 zeolites reveal that copper species are more uniformly speciated in the one‐pot synthesized sample (OP; Cu/Al=0.37), which demonstrates higher activity in a wide temperature range than does the ion‐exchanged sample (IE; Cu/Al=0.36).