An attempt was made to clarify the mechanism of a chain-extending reaction of NCO-terminated prepolymers in the synthesis of segmented poly(urethane–urea) using blocked ethylenediamine (EDA) with acetone (ACE). For this purpose, an ACE/EDA mixture was allowed to react with phenyl isocyanate (PhNCO) as a model of the prepolymer. The reaction of PhNCO with the ACE/EDA mixture, which was proved to contain ketimine and imidazolidine compounds by NMR measurements, gave 1,1′-ethylenebis[3-phenylurea] (M-Ur-1) as the main product; at the same time 1,3-diphenylurea (1,3-DPU) was assumed to be formed as a side-reaction product between PhNCO and H2O, inevitably existing in the mixture as the result of condensation. From a considerable increase in the yield of M-Ur-1 upon the addition of an excess amount of H2O to the reaction system, H2O was elucidated to participate in the acceleration of the main reaction, giving M-Ur-1 as well as in the side reaction, yielding 1,3-DPU. The excess H2O added to the system might preferentially facilitate the former reaction, rather than the latter.