We carried out a combined study using surface tension, phase-sensitive frequency generation (SFG) vibrational spectroscopy, and MD simulations to investigate the industrially relevant zwitterionic surfactant N-dodecyl-N, N-dimethyl-3-ammonio-1-propane sulfonate (DDAPS) on water surface. The SFG Im(chi((2))) spectra showed that the interaction between DDAPS and water was different from those between biologically relevant zwitterionic phospholipids and water. While zwitterionic phospholipids were found to be anionic-like and flipped water molecules with their OHs pointing toward the air, DDAPS oriented water molecules with their OHs mostly pointing toward the liquid water. We built a new force field for the MD simulation which produced the correct surface tension of water with various DDPAS coverage. The MD simulation showed that the head groups of DDPAS were nearly parallel to the water surface. When the surface coverage of DDPAS was increased, the averaged tilting angle of DDPAS's tails decreased, but it had little effect on the orientation of the headgroup. The sulfobetaine zwitterionic surfactant was found to be more cationic-like because the positively charged group was more capable of orienting interfacial water.