Amassing remarkable properties, silicones are practically indispensable in our everyday life. In most classic applications, they play a passive role in that they cover, seal, insulate, lubricate, water-proof, weather-proof etc. However, silicone science and engineering are highly innovative, seeking to develop new compounds and materials that meet market demands. Thus, the unusual properties of silicones, coupled with chemical group functionalization, has allowed silicones to gradually evolve from passive materials to active ones, meeting the concept of “smart materials”, which are able to respond to external stimuli. In such cases, the intrinsic properties of polysiloxanes are augmented by various chemical modifications aiming to attach reactive or functional groups, and/or by engineering through proper cross-linking pattern or loading with suitable fillers (ceramic, magnetic, highly dielectric or electrically conductive materials, biologically active, etc.), to add new capabilities and develop high value materials. The literature and own data reflecting the state-of-the art in the field of smart silicones, such as thermoplasticity, self-healing ability, surface activity, electromechanical activity and magnetostriction, thermo-, photo-, and piezoresponsivity are reviewed.