Smart materials and devices play an increasingly important role in improving modern life due to their richer functions, enhanced controllability, and improved biocompatibility. Herein, calcium silicate hydration (C-S-H) is integrated with layered [Co(NCS)2(pyrazine)2]n metal-organic frameworks (Co-MOF) and polymeric skeleton to fabricate the smart building material (M-C-S-H). C-S-H was anchored on the polymeric skeleton to reinforce the network structure for enhanced mechanical strength and toughness. Simultaneously, the highly porous skeleton structure enables the uniform distribution of layered Co-MOF, which could maintain its molecular form to endow the M-C-S-H with the photoresponsive color-switching performance. The M-C-S-H as a smart building material exhibits the color change between light blue and black blue upon near-infrared illumination on/off within a wide temperature range to achieve personalized wall and building decoration. Taking advantage of the low cost, rapid response, outstanding reversibility, and good color stability, M-C-S-H could provide lively, dynamic, and changeable decorating effects for walls and buildings. The smart building material, which is composed of calcium silicate hydration, layered metal-organic frameworks, and polymeric skeleton, exhibits the color change between light blue and black blue, upon near-infrared illumination on/off within a wide temperature range, achieving the lively, dynamic, changeable decorating effects for walls and buildings.image (c) 2024 WILEY-VCH GmbH