The copper hydroxy layered hybrids, Cu2(OH)3X, whereX=p−(phenylazo)-benzoate 1 andX= 8-((p−(phenylazo)phenyl)oxy)octanoate 2, were prepared. The material 1 is paramagnetic with an antiferromagnetic interaction above 3 K, while 2 becomes a weak ferromagnet below ca. 10 K. In 2 thetrans-to-cisisomerization reaction of the interlayer azobenzene moiety takes place by UV-light illumination, although the photoreaction is irreversible. There is little change in the magnetic properties, caused by the photoreaction.