Bicyclo[1.1.1]pentane　(BCP),　recognized　as　a　bioisostere　for　para-disubstituted　benzene,　has　gained　widespread　interest　in　drug　development　due　to　its　ability　to　enhance　the　physicochemical　properties　of　pharmaceuticals.　In　this　work,　we　introduce　a　photoinduced,　halogen　bonding-initiated,　metal-free　strategy　for　synthesizing　various　BCP　derivatives.　This　method　involves　the　generation　of　nucleophilic　α-aminoalkyl　radicals　via　halogen-bonding　adducts.　These　undergo　selective　radical　addition　to　[1.1.1]propellane,　yielding　electrophilic　BCP　radicals　that　subsequently　participate　in　polarity-matched　additions,　culminating　in　the　difunctionalization　of　bicyclopentane.　The　versatility　and　practicality　of　this　metal-free　approach　are　underscored　by　its　broad　substrate　scope,　which　includes　late-stage　functionalization　and　a　series　of　valuable　transformations,　all　conducted　under　mild　reaction　conditions.　©　2024　Wiley-VCH　GmbH.