 Novel goethite (α-FeOOH) corner-truncated tetragonal prisms (CTPs) with a length of about 1 μm and a width of about 200 nm have been synthesized by a hydrothermal method. The morphology, structure and electrochemical properties of CTPs are systematically studied. The obtained α-FeOOH CTPs exhibit high-quality single-crystalline nature. In addition, the single α-FeOOH corner-truncated tetragonal prism (CTP) is enclosed by six side facets, two {020} and four {110}. Depending on the reaction time, two different types of top-endings, one flat or two canted facets, are obtained. The formation of α-FeOOH is associated with the growth and subsequent phase transformation of β-FeOOH. The CTP contributes to structural stability and avoids the common pulverization process of electrodes. In addition, tiny crystallites are generated during the cycle, which increase the contact area between the electrode and electrolyte. Therefore, the α-FeOOH CTPs electrode displays excellent cycling performance with a reversible specific capacity of 870 mAh g−1 at 100 mA g−1 after 100 cycles.