A new method for studying the effect of pH on the polysiloxane network formation using electric fields is presented. The kinetic data obtained using these experiments indicates that the two-step interfacial polycondensation of silanes is strongly dependent on the pH, and the mechanism is essentially different at low and neutral to high values of pH. Very rapid hydrolysis followed by moderate rates of condensation are observed at neutral and high pH. The rate of hydrolysis is drastically reduced, while that of condensation is slightly lowered at low pH as compared to that at high values of pH. The slow hydrolysis reaction at low pH is then exploited to synthesize nonspherical microcapsules. Nonspherical polysiloxane microcapsules with varying aspect ratios from 1.05to 1.97 are synthesized by controlling the applied electric field.