Three new copper azide compounds, [Cu5(N3)10(N‐2AE‐1,3‐DAP)2] (I), [Cu5(N3)10(N‐3AP‐1,3‐DAP)2] (II), and [Cu7(N3)16(1‐(2‐AE)PIP‐H)2] (III) {where N‐2AE‐1,3‐DAP = N‐2‐aminoethyl‐1,3‐propanediamine, N‐3AP‐1,3‐DAP = N‐3‐aminopropyl‐1,3‐propanediamine, and 1‐(2‐AE)PIP = 1‐(2‐aminoethyl)piperazine} have been prepared by employing aliphatic amine molecules as coordination blocking amines. All the structures are built up by copper azide units linked through a copper–amine metalloligand, forming two‐dimensional layers. Compounds I and II have linear copper azide chains, whereas compound III has Cu5 linear units. The structures of I and II are identical except for the blocking amine molecule. The blocking amine molecule in III is protonated, which is rarely observed. Magnetic studies indicate antiferromagnetic behavior with possible metamagnet‐like features in all the compounds.