Novel anion exchange hybrid materials were developed by the insertion of poly(diallymethylammonium chloride) (PDDACl) and poly(allylamine hydrochloride) (PAHCl) polyelectrolytes into V2O5 interlayer spaces using hydrothermal treatment and were used to host an anionic cyanine dye. A systematic study of the hybrid material synthesis by direct in situ reaction of PDDACl and PAHCl polycations with V2O5 powders showed that the interlayer space of V2O5 expands from 0.44 nm to 1.40 nm and 1.80 nm upon intercalation of PDDACl and PAHCl polyelectrolytes, respectively. X-ray photoelectron spectroscopy and DR UV-Vis-NIR spectroscopy revealed that some V' sites were reduced to V' during the intercalation of the polyelectrolytes, these acted as both charge balancing entities for the negative oxide sheets and carriers for exchange sites located in the V2O5 interlayer space. The interlayer separation is consistent with the existence of coiled conformation of the polycations. The hybrid materials produced [PDDACl](0.24)[PDDA](0.29)V2O5 and [PAHCl](0.28)[PAH](0.47)V2O5, exhibited approximately 45.0% and 37.0% of chloride ions still available for anionic exchange, respectively. These materials were used to encapsulate a cyanine anionic dye. The presence of the dye was evidenced in the [PDDACL](0.24)[PDDA](0.29)V2O5 by significant fluorescence, with emission peak centered at 617 nm. C) 2011 Elsevier Inc. All rights reserved.