A surprising inversion of chirality of the -ITV zeolite framework is observed when the ethyl group of the enantiopure N,N-ethyl-methyl-pseudoephedrinium organic structure-directing agent is replaced by a benzyl or 2-methylbenzyl group, keeping the same molecular absolute configuration. Interestingly, chiral zeolite materials obtained with these new benzyl-containing cations reach unprecedentedly high enantiomeric excesses up to 55%.