Poly( urethane urea)s with hard segments derived only from diisocyanate linked via urea linkages were synthesized using a new and simple one-pot method. The creation of urea linkages were done via creating the amine in situ by adding water in vapor phase slowly and continuously. This synthesis method eliminates the tedious control to approach stoichiometry, is less sensitive to impurities, involves no intermediate isolation steps, and does not involve any chain extender. A study using a two-armedpoly(epsilon-caprolactone) as soft segment and methyl 2,6-diisocyantohexanoate (LDI) as the hard segment was performed. The length of the hard segment was varied from 4.8 to 11.6 LDI units. Stress-strain measurements showed an increase in elastic modulus, 146 to 235 MPa, when increasing the hard segment length, while the elongation at break decreased, 980 to 548%. IR spectroscopy showed an increase in hydrogen bonding when increasing the hard segment length. The synthesis was also shown to be applicable to common diisocyanates such as HDI, TDI, and MDI.