A　new　core-shell　nanosphere　TiO2@CoAl-LDH　was　synthesized　and　applied　to　prepare　a　photocatalytic　cementitious　composite.　The　photocatalytic　performance　of　the　photocatalytic　cementitious　composite　was　evaluated　by　the　real-time　degradation　of　NOx　and　methylene　blue　under　continuous　UV-visible　light　irradiation.　X-ray　diffraction　(XRD),　Fourier　transform　infrared　spectroscopy　(FTIR),　isothermal　calorimetry,　Vickers　microhardness,　field　emission　scanning　electron　microscopy　(FESEM),　atomic　force　microscopy　(AFM)　and　thermal　gravimetry　(TG)　were　employed　to　analyze　the　effects　of　TiO2@CoAl-LDH　on　early　cement　hydration,　localized　morphology,　and　microscopic　mechanical　properties　of　the　photocatalytic　cementitious　composites.　The　results　showed　that　the　newly　synthesized　core-shell　nanosphere　TiO2@CoAl-LDH　can　achieve　a　significant　utilization　of　solar　light　in　the　whole　wavelength　range　and　thus　exhibit　an　overall　better　photocatalytic　performance　compared　to　the　traditional　photocatalyst　TiO2,　particularly　when　an　appropriate　mix　dosage　was　applied　in　cementitious　composite.