Here,　we　report　a　feasibly　prepared　chiral　donor-acceptor　(D-A)　binaphthalene　imide　scaffold　with　locked　conformation,　exhibiting　significantly　improved　luminescent　performance　compared　with　its　open　conformation　species.　The　C1-symmetrical　chiral　imide　based　on　a　1,1′-binaphthol　(BINOL)　backbone　could　be　synthesized　on　the　gram　scale　with　only　silica　column　chromatography　resolution,　which　gave　a　photoluminescence　quantum　yield　(PLQY)　of　about　6%.　Further　configuration　rigidification　by　etherification　of　the　BINOL　backbone　with　a　series　of　alkane　linkers　showed　enhanced　PLQY　of　up　to　37%　and　turned　on　circularly　polarized　luminescence　(CPL).　Moreover,　the　photophysical　data　and　theoretical　calculations　revealed　that　the　enhanced　molecular　orbital　overlap　and　spin-orbital　coupling　of　these　locked　chiral　imides　led　to　the　activation　of　the　X-ray　excited　luminescence　(XEL)　property,　which　was　successfully　applied　in　an　X-ray　radiography　model.　This　work　not　only　provides　a　methodology　for　synthesizing　novel　chiral　D-A　scaffolds　but　also　highlights　the　potential　of　conformation　locking　strategy　in　achieving　multifunction　luminescence　for　axially　chiral　π-conjugated　molecules.　©　2024　American　Chemical　Society.