The　visible　light-driven　photoswitches　are　attracting　widespread　attention,　but　it　is　challenging　to　leverage　their　phototriggered　structural　changes　to　regulate　dynamic　bonds,　assemblies,　and　materials.　Herein,　we　incorporated　reversible　covalent　sites　of　aldehyde　ring-chain　tautomers　into　all-visible-light　azobenzenes　toward　a　versatile　platform　for　light-controlled　formation/exchange　of　dynamic　C—N　bonds　from　secondary　amines.　The　movement　of　ring-chain　equilibrium　was　attained　via　manipulating　intramolecular　multiple　hydrogen　bonding　from　E/Z　configurational　isomers.　Such　structural　regulation　further　enabled　photocontrolled　kinetics　for　the　formation　and　exchange　reactions　of　cyclic　hemiaminal　ethers　from　secondary　amines　exhibiting　kinetic　rate　reversal　from　E/Z　isomers.　The　varied　capability　of　E/Z　configurational　isomers　in　engaging　in　multiple　hydrogen　bonds　of　azo　attached　carboxylate　with　ammonium　salt　accounts　for　the　difference.　Moreover,　the　photoswitching　performance　of　azobenzenes　in　different　solutions　was　readily　regulated　by　dynamic　covalent　reactions　with　amines.　The　dynamic　reactivity　control　with　visible　light　and　associated　mechanistic　foundation　add　into　the　collection　of　photoswitchable　dynamic　covalent　chemistry　and　would　lay　the　foundation　for　subsequent　biological　and　material　applications.　©　2025　SIOC,　CAS,　Shanghai,　&　WILEY-VCH　GmbH.