The unique alumophosphite reagent LAI(SH)(mu-O)P(OEt)(2) was prepared and used for the synthesis of the heterobimetallic alumophosphites [{kappa(2)-S,P-LAI(S)(mu-O)P(OEt)(2)}(2)Zn] and [{kappa(4)-S,O,O-LAI(SLi)(mu-O)P(OEt)(2)}(2)]. The first contains a rare example of two carbon-free five-membered heterocycles (Al-S-Zn-P-O) connected in a spiro fashion through the zinc atom, whereas the second possesses an unknown example of a coordination environment of a phosphite unit M-O-P(mu-OEt)(2)M with an uncoordinated lone electron pair on the phosphorus center.