The article presents a novel method for the synthesis of borylated bicyclo[2.1.1]hexanes via crossed [2 + 2]-cycloaddition, which allows for the preparation of a diverse range of structures that are not accessible by other methods. The presence of the C–B bond enables the synthesis of various substituents, enhancing the chemical space for drug development and agrochemicals. Additionally, the study discloses a rare photo-ene reaction that allows for the diastereoselective synthesis of trisubstituted borylated cyclopentanes. The mechanism of the photo-ene reaction is discussed, and guidelines for predicting reactivity are provided. The versatility of the synthesized borylated bicyclo[2.1.1]hexanes is demonstrated through various transformations, including oxidation, reductive amination, metal-free cross-coupling, and homologation. The article also explores the synthesis of more complex spirocyclic bicyclo[2.1.1]hexanes and their transformations, highlighting the potential of this method in drug and agrochemical synthesis.The article presents a novel method for the synthesis of borylated bicyclo[2.1.1]hexanes via crossed [2 + 2]-cycloaddition, which allows for the preparation of a diverse range of structures that are not accessible by other methods. The presence of the C–B bond enables the synthesis of various substituents, enhancing the chemical space for drug development and agrochemicals. Additionally, the study discloses a rare photo-ene reaction that allows for the diastereoselective synthesis of trisubstituted borylated cyclopentanes. The mechanism of the photo-ene reaction is discussed, and guidelines for predicting reactivity are provided. The versatility of the synthesized borylated bicyclo[2.1.1]hexanes is demonstrated through various transformations, including oxidation, reductive amination, metal-free cross-coupling, and homologation. The article also explores the synthesis of more complex spirocyclic bicyclo[2.1.1]hexanes and their transformations, highlighting the potential of this method in drug and agrochemical synthesis.