The effects of acidity of electrolyte (pH) on the hysteresis behavior, the specific surface area, and nanostructure morphology of electrolytic manganese dioxides (EMDs) have been studied by using the Barrett-Joyner-Halenda (BJH) analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) images analysis. EMD samples are electrodeposited at a variable pH (6 to 1) and many fixed pH (2, 3, 4, 5, and 6). Results indicate that pH play key roles in the characteristics of EMD. The samples obtained at low pH (2 and 3) show multi-branched morphology and represent a H4 hysteresis loop. At pH 4 and 5, a uniform and dense structure of MnO2 is obtained without hysteresis behavior. The sample electrodeposited at pH 6 shows a regular reticulate, that its adsorption-desorption isotherm show hysteresis behavior. By electrodeposition at a variable pH, the sample shows a cauliflower-like and multi-branched form. From the viewpoint of classification of isotherm, pH strongly affects on Type of isotherm. The results show that gamma-MnO2 is as main-product of electrodeposition and alpha-MnO2 and beta-MnO2 were obtained as side-product at low and high pH, respectively. (C) 2012 Elsevier B.V. All rights reserved.