The demand for electrochemical sensors with high sensitivity and reliability, fast response, and excellent selectivity has stimulated intensive research on developing highly active nanomaterials. In this work, freestanding 3D/Co 3 O 4 thorn-like and wire-like (nanowires) nanostructures are directly grown on a flexible carbon fiber paper (CFP) substrate by a single-step hydrothermal process without using surfactants or templates. The 3D/Co 3 O 4 thorn-like nanostructures show higher electrochemical activity than wire-like because of their high conductivity, large specific surface areas, and mesopores on their surface. The characterization of 3D/Co 3 O 4 nanostructures is performed by using high resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), X-ray photoelectron spec-