The geometrical rule of molecular packing parameters in a bolaamphiphile solution was tested with experimental results. By modifying the solution conditions to change the molecular packing parameters, the morphology of the aggregate was successfully manipulated in a single-chain bolaamphiphile, disodium phenyl-1,4-bis (oxyhexanoate) (i.e., C6PhC6Na2 solution). Micelle-vesicle-tube transformation was observed by changing the pH and the addition of NaBr or octanol. In the mixed systems of oppositely charged bola/surfactants, the molecular packing parameter's role is related to the mixing ratio.