Carbon electrodes form the basis of a variety of electroanalytical sensors, in part due to their low cost, wide potential range, and suitability for modification. A major research effort is underway in many laboratories to understand better the properties of carbon electrodes regarding electrocatalytic activity and other factors such as background current and electron transfer activity. One method of improving the performance of these electrode materials involves the application of pulses from a Nd:YAG or N2 laser, either during or prior to electrochemical use. Both electrochemical and spectroscopic probes indicate dramatic changes to the surface of the electrodes after the pulses. Raman spectroscopy of the electrode surface indicates damage to the carbon lattice, with an increase in intensity of the Raman band at 1360 cm−1. This band is active in crystallites of finite size, and indicates increased exposure of graphitic edge plane. Also, there is a dramatic increase (≥106×) in heterogeneous charge-transfer rates measured with redox benchmark probes [Fe(CN)6−3/−4, dopamine]. Mechanisms of electrode activation by the laser pulses can involve roughening of the electrode surface, or ablation or cleaning of the electrode. Scanning tunneling microscope (STM) images of graphite and glassy carbon surfaces before and after delivery of laser pulses of various energies show a roughening of the surface from the laser treatment, with the appearance of new features of submicron size. The graphite electrodes show a highly disrupted surface, with jagged features and high roughness factors, determined from the STM images. None of the types of features observed in the laser-activated regions of graphite electrodes have been previously observed in our laboratory, in the course of dozens of experiments involving the imaging of different samples and grades of fresh or mechanically damaged graphite electrodes.