This study was conducted to investigate the characteristics of the curling behavior of long-span pavement slabs under environmental loads. By developing and using finite element models of the long-span pavement slabs, the stress distribution and the effects of slab length, slab thickness, stiffness of underlying layers, and the restraints of the slab ends on the curling behavior were analyzed. In addition, the field experiments were performed with the actual long-span pavement slab to obtain the curling behavior of the real structure under environmental loads. As a result of this study, it was found that the vertical displacements of the long-span pavement slab along the centerline due to the curling behavior were zero except for the areas near the slab ends, and the curling stresses were maximum and constant where the displacements were zero. The slab length and the stiffness of underlying layers did not affect the maximum curling stresses. The restraints at the slab ends made the curling stresses occur near the slab ends, but did not much affect the maximum curling stresses.