The scientific challenges involved in the creation of organic-inorganic hybrid materials based on layered silicates with controlled morphological, optical and electronic properties have evolved considerable interest during the last few decades. The interlayer gap in the Bentonite clay provides an interesting, confined environment for the accommodation of the guest molecule at the nanoscale. Moreover, solid state reactions carried out using the reactants confined in clays, zeolites, silica, alumina or other matrices via microwave irradiation not only produce structures of controlled growth but bring down the handling costs due to simplification of experimental procedure which is important in terms of environmentally benign large scale industrial synthesis. This article highlights for the first time the effect of peroxides in controlling the properties of polycarbazole (PCz) within the Bentonite clay interlayer space in terms of morphology, spectral, and fluorescent properties synthesized through microwave-assisted solid-state intercalation. The orientation of the polymer within such restricted nanoscale environment is expected to be a significant solution for obtaining a better control of the molecular architecture. (C) 2013 Elsevier B.V. All rights reserved.