Catheter ablation in patients suffering from chronic arrhythmias often requires detailed knowledge of the specific myocardial anatomy underlying the catheter tip to guide the delivery of the ablating RF energy. Such information is often lacking in a clinical procedure. In this study, we present a proof-of-concept computational investigation into the potential for using an optical strategy, based-on diffuse optical reflectance, to provide quantitative anatomical measures of underlying myocardial wall thickness and presence of scar. In detailed Monte Carlo simulations of light scattering, significant changes in peak height and FWHM of radial profiles of diffusely reflected light were seen with both changes in tissue thickness and presence of underlying scar. Such changes were seen to occur to different degrees for different wavelengths of light. In conclusion, our findings suggest that examining the ratio of these changes between different wavelengths may provide the potential basis for an optical-catheter to map underlying cardiac anatomy and guide ablation in the clinic.