In order to compare the polarographic behaviour ofcisandtransaliphatic azoxy compounds, synthesis and polarographic study ofcisandtransazoxycyclohexanes are performed. Thecisform is a new compound obtained by photoisomerisation of thetranscompound. In acid medium the polarographic reduction process is the same for both forms: hydrazocyclohexane is the final reduction product. In alkaline medium thetransazoxy compound is electroinactive and thecisazoxy compound is reducible and leads to a mixture oftransazocyclohexane and hydrazocyclohexane.