Semiconductors　with　broadband　photoelectric　response　have　important　practical　needs　in　many　aspects　such　as　solar　energy　conversion,　photocatalysis,　and　photodetection.　We　synthesized　the　first　photochromic　semiconductive　hydrogen-bonded　organic　framework　(HOF),　[H-2(bpyb)](H2PO4)(2)center　dot　2H(2)O　(1),　using　the　polycyclic　viologen　cation　[H-2(bpyb)]　(bpyb　=　1,4-bis(tetrapyridyl)benzene).　After　1　s　of　xenon　lamp　irradiation,　compound　1　showed　a　visible　color　change　from　the　initial　yellowish　to　dark　purple　after　continuous　irradiation.　The　photoinduced　radical　product　has　an　absorption　band　covering　200-1700　nm,　which　is　wider　than　the　absorption　ranges　of　silicon　and　perovskites.　It　produced　photocurrent　when　irradiated　with　a　xenon　lamp　or　a　laser　(355,　532,　or　808　nm).　The　on/off　ratio　of　the　current　(I-irr/I-dark)　can　be　as　high　as　300　times　under　the　irradiation　of　the　808　nm　laser　with　a　power　of　1.9　W　cm(-2).　In　addition,　under　the　808　nm　light　source,　the　on/off　ratio　of　1B　is　35　times　that　of　1A.