Following a study on the morphological and structural properties of CdTe and CdZnTe layers grown by MOCVD on GaAs substrates of (h11) orientation and A or B polarity, the growth on (211) GaAs substrates misoriented toward (111) and (100) is investigated. High structural quality twin-free CdHgTe layers of near (525) orientation are obtained on (211) surfaces misoriented toward (111), while a misorientation toward (100) leads to a very high density of twins. These results are explained from the bond features at the growth interface.