Abstract: The disclosure describes Structured Biological Materials (“SBM”) adapted for use in emulsion-less multiphasic processes. The SBM is a substratum-microbial matrix combination, wherein the microbial matrix houses one or more natural or genetically-engineered microorganisms capable of catalyzing or performing reactions that occur in multiphasic environments. When used in an emulsion-less system, the SBMs should be able to maintain separation of the bulk phases sufficient to maintain the emulsion-less nature of the system. The disclosure also provides methods of using the SBMs, for example in performance of multiphasic reactions, such as emulsion-less biphasic liquid/liquid reactions. This disclosure also provides multiphasic membrane reactors wherein an SBM functions as the membrane, such as emulsion-less biphasic reactors wherein an SBM functions as the biphasic membrane.