Contact angle relaxation was measured for captive. air bubbles placed on solid surfaces of varying degrees of heterogeneity, roughness, and stability, in water.:The experimental results indicate that both advancing and receding contact angles undergo, slow relaxation in these water-air-solid systems, due to instabilities of the three-phase contact line region. It is shown that the advancing contact angle decreases and the receding contact I angle increases for many systems over a period of a few hours. Also, examples of reverse progressions are reported. Additionally, in extreme cases, the, contact angle oscillates down and up, over and over again, preventing the system from stabilization/equilibration: Four different mechanisms are-proposed to explain the contact angle relaxation. The se include (i) pinning of the three-phase contact line and its slow evolution; (ii) the formation of microdroplets on the solid surface and their coalescence with the base of the gas bubble, which causes dynamic behavior of the three-phase contact line; (iii) deformation of the solid surface and its effect on the apparent contact angle; and (iv) chemical instability of the solid.