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A promising avenue of research in materials science is to follow the strategies used by Mother Nature to fabricate ornate hierarchical structures as exemplified by organisms such as diatoms, sponges and magnetotactic bacteria. Some of the strategies used in the biological world to create functional inorganic materials may well have practical implications in the world of nanomaterials. Therefore, the strive towards exploring nature's ingenious work for designing strategies to create inorganic nanomaterials in our laboratories has led to development of biological and biomimetic synthesis routes over the past decade or so. A large proportion of these relentless efforts have explored the use of those microorganisms, which are typically not known to encounter these inorganic materials in their natural environment. Therefore, one can consider these microorganisms as 'unusual' for the purpose for which they have been utilized - it is in this context that this review has been penned down. In this extensive review, we discuss the use of these 'unusual' microorganisms for deliberate biosynthesis of various nanomaterials including biominerals, metals, sulfides and oxides nanoparticles. In addition to biosynthesis approach, we have also discussed a bioleaching approach, which can provide a noble platform for room-temperature synthesis of inorganic nanomaterials using naturally available raw materials. Moreover, the unique properties and functionalities displayed by these biogenic inorganic materials have been discussed, wherever such properties have been investigated previously. Finally, towards the end of this review, we have made efforts to summarize the common outcomes of the biosynthesis process and draw conclusions, which provide a perspective on the current status of the biosynthesis research field and highlights areas where future research in this field should be directed to realize the full potential of biological routes towards nanomaterials synthesis. Furthermore, the review clearly demonstrates that the biological route to inorganic materials synthesis is not merely an addition to the existing list of synthesis routes; biological routes using 'unusual' microorganisms might in fact provide an edge over other nanomaterials synthesis routes in terms of their eco-friendliness, low energy intensiveness, and economically-viable synthesis. This review has significant importance for colloids and interface science since it underpins the synthesis of colloidal materials using 'unusual' microorganism, wherein the role of biological interfaces for controlled synthesis of technologically important nanomaterials is clearly evident., (Copyright © 2012 Elsevier B.V. All rights reserved.)