In this work, we describe the stoichiometrically controlled self-assembly process of tetraurea calix[4]pyrrole 1 with a polar neutral guest, trimethylamine N-oxide or beta-alanine betaine, and methyltrioctylammonium chloride salt into two supramolecular architectures differing in morphology and stoichiometry. Whereas an equimolar solution of tetraurea calixpyrrole 1, the polar guest and MTOACl produces a four-particle inclusion assembly, the mixture of the same components in a 2:1:1 molar ratio induces the formation of a dimeric capsular assembly displaying multiple guests orderly co-encapsulated. The influence of other polar guests and ammonium salts on the self-assembly process is also described.