Highly uniform 3D MnV2O6 nanostructures modified by oxygen functional groups (-COO-) were successfully prepared in large quantities by an approach involving preparation of vanadyl ethylene glycolate as the precursor. The growth and self-assembly of MnV2O6 nanobelts and nanorods could be readily tuned by additive species and quantities, which brought different morphologies and sizes to the final products. With a focus on the regulation of structure, the formation process of 3D architectures of MnV2O6 by self-assembly of nanobelts was followed by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The consecutive processes of vanadyl ethylene glycolate and benzoyl peroxide assisted formation of layered structure Mn0.5V2O5 center dot nH(2)O, growth of aligned MnV2O6 nanobelts, and oriented assembly were proposed for the growth mechanism. The band gap vs. different morphology was also studied. Optical characterization of these MnV2O6 with different morphologies showed direct bandgap energies at 1.8-1.95 eV. The adsorption properties of 3D MnV2O6 nanostructures synthesized under different conditions were investigated through the removal test of Rhodamine B in aqueous water, and the 3D nanostructures synthesized with 30 g L-1 benzoyl peroxide showed good adsorption capability of Rhodamine B. (C) 2012 Elsevier Ltd. All rights reserved.