Although the search for new zeolites has traditionally been based on trial and error, more rational methods are now available. The theoretical concept of inverse σ transformation of a zeolite framework to generate a new structure by removal of a layer of framework atoms and contraction has for the first time been achieved experimentally. The reactivity of framework germanium atoms in strong mineral acid was exploited to selectively remove germanium-containing four-ring units from an UTL type germanosilicate zeolite. Annealing of the leached framework through calcination led to the new all-silica COK-14 zeolite with intersecting 12- and 10-membered ring channel systems. An intermediate stage of this inverse σ transformation with dislodged germanate four-rings still residing in the pores could be demonstrated. Inverse σ transformation involving elimination of germanium-containing structural units opens perspectives for the synthesis of many more zeolites.