Spontaneously adsorbed organic films can drastically influence the electrochemical reactivity of carbon materials. We report here a combined electrochemical and scanning force microscopic (SFM) study of anthraquinone 2,6-disulfonate films adsorbed to ordered graphite electrodes. The cyclic voltammetric signature of adsorbed 2,6-AQDS depends on the bulk solution concentration of the adsorbate. Films formed from lower concentrations (<10 mu M) exhibit near ideal voltammetry for a surface-bound redox system while the voltammetry of layers formed from higher concentration solutions (>10 mu M) is less ideal and consists of multiple waves. One of these waves is anomalously sharp, characteristic of significant intermolecular interactions within the adsorbate layer. In situ SFM images reveal differences in the two-dimensional structure of 2,6-AQDS films on graphite as a function of concentration. High-resolution lateral force images aid in the correlation of the structure of the adsorbate layers with their electrochemical response. We also discuss the inconsistency between the voltammetrically measured surface coverage and that observed in SFM images.