Two azide-bridged chiral Cu(II) compounds, [Cu(R,R-dacy)(N3)2]n (R,R-dacy = trans-(1R,2R)-diaminocyclohexane) and [Cu(S,S-dacy)(N3)2]n (S,S-dacy = trans-(1S,2S)-diaminocyclohexane), with two-dimensional layer structures exhibiting end-to-end and end-on azide bridging patterns, were prepared and among them was examined to show a field-induced spin-flop transition.