Electron-rich and poor BN-heterocycles with benzyl-pyridyl backbones and two bulky aryls on the boron (Ar = tipp, BN-1, Ar = MesF, BN-2) have been found to display distinct molecular transformations upon irradiation by UV light. BN-1 undergoes an efficient photoelimination reaction forming a BN-phenanthrene with Phi(PE) = 0.25, whereas BN-2 undergoes a thermally reversible, stereoselective, and quantitative isomerization to a dark colored BN-1,3,5-cydooctatriene (BN-1,3,5-COT, BN-2a). This unusual photoisomerization persists for other BN-heterocycles with electron-deficient aryls such as BN-3 with a benzyl-benzothiazolyl backbone and Mes(F) substituents or BN-4 with a benzyl-pyridyl backbone and two C6F5 groups on the boron. The photoisomerization of BN-4 goes beyond BN-1,3,5-COT (BN-4a), forming a new species (BN-1,3,6-COT, BN-4b) via C-F bond cleavage and [1,3]-F atom sigmatropic migration. Computational studies support that BN-4a is an intermediate in the formation of BN-4b. This work establishes that steric and electronic factors can effectively control the transformations of BN-heterocycles, allowing access to important and previously unknown BN-embedded species.