The research project Fraunhofer Cluster of Excellence “Programmable Materials” aims to develop new materials that can change their properties according to defined boundaries. This article describes the development and use of a novel programmable phase change material (PCM) for latent heat storage applications. At the moment, these PCMs have a programmable trigger mechanism incorporated that activates the crystallization of the material as a reaction to a defined stimulus so that the stored heat is released. In future development stages, programmability is to be integrated on the material level. The latent heat storage that is based on PCMs can be recharged by using the energy of the sun. As an example, for a possible application of such a material, the use of a novel programmable PCM in greenhouses to support heating energy reduction or to reduce the risk of frost is explained. Using the hygrothermal simulation tool WUFI® Plus, the effects in greenhouse constructions without and with commercially available or novel programmable PCMs are calculated and presented in the present article. The calculations are based on the material data of calcium chloride hexahydrate (CaCl2-6H2O), as this material serves as a basic material for the development of programmable PCM compositions. The results of the simulations show a positive impact on the indoor temperatures in greenhouses in view of the risk of frost and the reduction of heating energy. Thus, the vegetation period can be extended in combination with a lower energy load. By an eligible actuation mechanism, an inherent material system for temperature control can be created.