Solar-driven　hydrogen　evolution　from　urea-rich　wastewater　is　a　highly　promising　energy-environment　bi-functional　synthetical　solution,　while　the　intrinsic　contradict　between　spectral　energy　quantity　and　quality　of　sunlight　limits　the　existing　wavelength-dependent　technologies.　Herein,　we　report　the　first　demonstration　of　concentrated　photo-thermo-catalysis　(CPTC)　technology　that　regulates　the　spectral　energy　quantity　and　quality　and　creates　the　synergy　between　photon　and　thermal　effects　to　achieve　full-spectrum　solar　harmonic　conversion　of　aqueous　urea　and　urine　into　hydrogen.　The　50%　enhanced　CPTC　performance　compared　with　sole　photo-/thermo-catalysis　is　achieved　due　to:　(1)　Catalyst　structure　optimization.　Single　Cu　atom　and　2D　Cu　raft　are　acquired　on　defect-rich　TiO2　support　by　photo-thermo-organized　metal-support　interaction;　(2)　Reaction　pathway　expansion.　The　breakthrough　against　thermodynamic　barrier　of　urea　to　hydrogen　is　realized　by　the　novel　cascade　reactions　of　thermally-triggered　urea　hydrolysis　and　thermally-assisted　ammonia　photo-decomposition.　The　technological　viability　is　convincingly　presented　through　outdoor　test　with　artificial　urine　under　real　sunlight.　©　2022　Elsevier　B.V.