Herein, we report the successful application of bicyclo[1.1.0]butyl radical cations to [2π+2σ] cycloaddition reactions to generate a unique selection of BCH structures (Fig. ). The most notable features of this strategy are the breadth of alkene classes that can be employed and the remarkable levels of regio-and diastereoselectivity that can be achieved using single-electron oxidation as the activation mode for BCB. A rigorous experiment-based mechanistic study, in conjunction with DFT computation, was undertaken in order to better understand this process and illuminate how these strained radical cations interact with alkenes. Consequently, we believe that the work described here can serve as a platform from which further studies into the potential synthetic applications of BCB radical cations can be built upon.