Semiconductor　conductivities　depend　largely　on　the　crystal　structures　and　the　associated　electronic　structures.　If　the　electronic　structures　can　be　switched　reversibly　in　the　same　crystal　structure,　then　a　drastic　conductivity　change　may　be　controllable.　The　effect　of　electron　transfer　(ET)　on　semiconductor　conductivity　remained　elusive　so　far.　In　this　work,　a　series　of　two　pillared　inorganicorganic　hybrid　photochromic　semiconductors　(PSCs),　[(CQ)Pb3X6(H2O)]·2H2O　[X　=　Cl　(1)　and　Br　(2),　CQ　=　N-4,4′-bipyridiniopropionate　(viologen)],　with　II-stacking　viologen　π-aggregates,　are　constructed　by　a　bottom-up　self-assembly　strategy　through　inorganic　skeleton-directed　intercalation　and　intermolecular　noncovalent　interaction.　The　conductivities　are　abnormally　＇invariant＇after　photoinduced　ET,　breaking　the　convention　that　the　generation　of　radicals　favors　conductivity.　The　abnormally　＇invariant＇conductivities　are　mainly　derived　from　approximate　electronic　couplings　before　and　after　ET　between　II-stacking　viologen　π-aggregates.　©　2022　American　Chemical　Society.