This paper describes the preparation, characterization, and electrochemical properties of reduced graphene sheet films (rGSFs), investigating especially their electrochemical behavior for several redox systems and electrocatalytic properties towards oxygen and some small molecules. The reduced graphene sheets (rGSs) are produced in high yield by a soft chemistry route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction. Transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy clearly demonstrate that graphene was successfully synthesized and modified at the surface of a glassy carbon electrode. Several redox species, such as Ru(NH3)63+/2+, Fe(CN)63−/4−, Fe3+/2+ and dopamine, are used to probe the electrochemical properties of these graphene films by using the cyclic voltammetry method. The rGSFs demonstrate fast electron-transfer (ET) kinetics and possess excellent electrocatalytic activity toward oxygen reduction and certain biomolecules. In our opinion, this microstructural and electrochemical information can serve as an important benchmark for graphene-based electrode performances.