Novel double network (DN) hydrogels were prepared via atom transfer radical polymerization (ATRP) of the first network using two different initiators, and followed by ultraviolet (UV) photo-initiated polymerization for the second network. The first networks DN hydrogels were prepared by using two different initiators; one is a one-side initiator, and the other is a double-side initiator. The mechanical properties of various DN gels, such as water content and compressive strength, were studied. The network structure of the DN hydrogels was also characterized by dynamic light scattering. Thus, we demonstrated that the ATRP method is useful to control the network structure of the first network for DN gels. Extensive inhomogeneous structure of the first network wits obtained by ATRP method and increased both the swelling degree and softness of DN gels. (C) Koninklijke Brill NV, Leiden, 2009