Vesicles　obtained　by　the　self-assembly　of　asymmetric　tetrablock　copolymers　are　a　class　of　materials　with　fascinating　properties.　However,　simple　strategies　to　synthesize　asymmetric　tetrablock　copolymers　are　limited.　Herein,　we　have　designed　and　synthesized　an　initiator　which　generates　radicals　by　either　heating　or　photoirradiation.　Taking　the　advantages　of　organocatalyzed　reversible　complexation　mediated　radical　polymerization　which　has　lower　energy　requirements,　milder　reaction　conditions,　and　reduced　generation　of　hazardous　byproducts,　a　three　steps　synthetic　route　following　“photo-photo-thermal”　initiation　condition　for　the　preparation　of　asymmetric　CABC　tetrablock　copolymers　with　controllable　molecular　weight,　precise　block　composition　and　low　polydispersity　was　developed.　©　2023　Fudan　University