Layer- and tunnel-structured manganese oxide nanomaterials are important because of their potential applications in industrial catalysis. A novel soft chemistry method was developed for the synthesis of inorganic cryptomelane nanomaterials with high surface area. Bright field transmission electron microscopy (BF-TEM) and high-resolution transmission electron microscopy (HRTEM) techniques were employed to characterize this nanomaterial. A nanosized material with fibrous texture comprised of 140–160 nm striations was identified by BF-TEM imaging. HRTEM images show multiple atomic morphologies such as “helix-type,” “doughnut-like,” and tunnel structures lying on different crystallographic planes. The crystallographic parameters of this material were analyzed and measured by X-ray powder diffraction (XRD) showing that the synthesized nanomaterial is single phased and corresponds to cryptomelane with major diffraction peaks (for 10° < 2θ < 60°) at d-spacing values of 6.99, 4.94, 3.13, 2.40, 2.16, 1.84, 1.65, and 1.54 Å. A “doughnut-like” crystal structure was confirmed based on the crystallographic data. Structure and lattice parameters refinement was performed by XRD/Rietveld analysis. Simple simulation of HRTEM images and selected area diffraction patterns were applied to interpret the HRTEM images as observed.