Bicyclo[1.1.1]pentanes (BCPs) play a crucial role in drug discovery research as C(sp3)-rich bioisosteres of benzene rings. However, the preparation of BCPs with strong alkane C(sp3)-H bonds has not been reported to date. In this study, we reported a method for light-induced benzyl alcohol functionalization of [1.1.1]propellane with aliphatic hydrocarbons (which have not previously been explored for this purpose) and aldehydes under metal- and photocatalyst-free conditions. The BCP products could be transformed into various useful derivatives, demonstrating the utility of the method. Notably, we achieved the synthesis of functionalized BCPs with simple alkanes.