Using diethyl ether as a co-solvent, a non-stable interface of biphasic oil-water system (the so-called oil-water two-phase (OWTP) system) was employed in the preparation of mesostructured silicas with diversified particle morphologies. By adjusting the molar ratios of H2O:C2H5OC2H5:NH3 center dot H2O and the alkalinity of the OWTP system, several product morphologies could be obtained under different reaction conditions. On the other hand, different product morphologies with distinct structural properties could be obtained at a specific reaction condition, indicating that product morphology varied upon intrinsic characteristics of non-equilibrium processes in the system as well. There are six kinds of product morphologies in our results. In the biphasic region the morphotypes such as vesicles, slices, and spheres were widely distributed. Multi-lamellar fragments were formed under relatively strong alkaline conditions and at a high proportion of diethyl ether (>41%). bi-continuously phased fragments were observed in the weak alkaline conditions and medium proportion between diethyl ether and water. In the single-phase region, hexagonally ordered MCM-41, plain sheets of MCM-48, as well as smooth and plain slices with worm-like pore structures were formed with bi-modal pore-size distribution structure. Based on HRTEM analysis, these structural features were rationalized being derived from fragments that originated from the oil/water interface. Apparently, the product morphosynthesis resulted from a combination of fluid theological distortions and reconstructive reaction fields. With a systematic approach we have established the reaction phase diagram of the system, which enabled us to define the structural properties and to classify the morphology of the products for nomenclatural purposes in studying OWTP systems. (c) 2007 Elsevier Inc. All rights reserved.