Pure shear deformation reveals the significant differences in elastic properties of the poly(vinyl alcohol) (PVA) gels with almost identical initial modulus, but with different types of crosslinks, physical crosslinks formed by microcrystallites and chemical crosslinks made of covalent bonds. The ratio of the two principal stresses steeply increases with elongation in the physical gels, while that remains almost constant independently of stretching in the chemical gels. The marked growth of the stress ratio with elongation in the physical gels leads to the negative values of the derivative of the elastic free energy (W-2) with respect to the second invariant of the deformation tensor in the whole range of deformation, which is firstly observed for elastomeric materials. By contrast, the chemical gels exhibit the positive values of W-2 like most chemically crosslinked rubbers. Among the existing theories of rubber elasticity, the classical non-Gaussian three-chain model considering the effect of finite chain-length is qualitatively successful in accounting for the steep increase of the stress ratio and the negative values of W-2 in the physical gels, although it fails to reproduce the large difference in the stress-strain behavior among uniaxial, pure shear and equibiaxial deformations. These features of the physical gels are expected to stem from the structural characteristics such as fewer amounts of slippery-trapped entanglement along network strands compared to the chemical PVA gets. (c) 2006 Elsevier Ltd. All rights reserved.