Bilayer structures in catanionic systems experimentally showed peculiar mechanical behavior. The observed increase in the bending stiffness is supposedly connected to additional hydrogen bonds forming between anionic headgroups. With a simple model, we can explain the extreme sensitivity of the bending stiffness of the membrane on the molar ratio of the charged molecules. This effect is further amplified by the sandwichlike structure of the membrane, where the apolar core separating the headgroups acts via a kind of lever-arm principle. As a consequence of these combined effects, the model membrane changes from a soft behavior with bending rigidities on the order of 10k(B)T to an extremely stiff membrane with a bending stiffness more than 2 orders of magnitude larger where most of this change occurs within a molar ratio interval smaller than 0.1.