Derivatives of 1,2-dihydro-1,2-azaborinines generally undergo selective photochemical electrocyclic ring-closure reactions to the corresponding Dewar isomers (2-aza-3-borabicyclo[2.2.0]hex-5-ene). Depending on the substitution pattern, these photoreactions can also yield benzvalene (3-aza-4-boratricyclo[3.1.0.02.6]hexane) analogues. Here, we report the synthesis of 1,2,3,5-tetrasubstituted dihydroazaborinines by transition-metal-catalyzed late-stage functionalization and the investigation of their photophysical and photochemical properties using transient absorption spectroscopy. The introduction of aryl groups at the 3- and 5-positions induces a pronounced bathochromic shift of the absorption maximum. Under broad-spectrum irradiation (280–400 nm), quantitative conversion to the benzvalene isomer can be achieved. The initial photoisomerization proceeds via excitation to the short-lived singlet excited state (S1) yielding the Dewar isomer, whereas the subsequent conversion of this intermediate occurs through a long-lived excited state. Notably, the second isomerization step is accompanied by an interchange of the carbons C3 and C4. Once formed, the benzvalene isomers exhibit exceptional thermal stability. Cycloreversion to the Dewar isomer and even to the dihydroazaborinine structure can be triggered photochemically through targeted excitation and during both processes the substituents return to the C3 and C5 positions. The thermal cycloreversion of the benzvalene isomer can yield either the educt BN-benzene isomer (1,2,3,5-substitued) or its 1,2,4,5-substituted isomer. Computational studies revealed a stepwise mechanism for the thermal back reaction reforming the educt, while a concerted, energetically less-favorable pathway leads to the 1,2,4,5-substituted analogue.