Bacillus-shaped bilayer vesicles of nanoscale size are very rare structures of stable surfactant self-assembly, because they are both thermodynamically and electrostatically unfavorable in solution. It is evidently demonstrated that appropriately aqueous mixtures of single-tailed cationic and anionic (catanionic) surfactants can produce rigidly bacillus-shaped bilayer vesicles with both flat parts and bent edges. The crucial requirement for forming bacillus-shaped bilayer vesicles is the use of cationic surfactants with relatively hydrophobic [FeCl3Br]- as counterions. [FeCl3Br]- can strongly associate with cationic surfactants to partition into the hydrophobic bilayer of bacillus-shaped bilayer vesicles, significantly increasing the edge energy of cationic surfactants to make them distribute in the low curvature part of bilayers. This causes the formation of bacillus-shaped bilayer vesicles, but not completely bent spherical vesicles, in the case of cationic surfactant excess. The specificity of hydrophobic counterions, [FeCl3Br]-, could also make the catanionic mixtures do not precipitate at the stoichiometric point. This new self-assembly on catanionic systems is culminated in the discovery of beautifully structured colloidal objects which are of practical use for molecular templating and controlled drug or DNA release.