Energy flux parameterization was effected for the city of Athens, Greece, by utilizing two approaches, the Local- Scale UrbanMeteorological Parameterization Scheme(LUMPS) and the Bulk Approach (BA). In situ acquired data are used to validate the algorithms of these schemes and derive coefficients applicable to the study area. Model results from these corrected algorithms are compared with literature results for coefficients applicable to other cities and their varying construction materials. Asphalt and concrete surfaces, canyons and anthropogenic heat releases were found to be the key characteristics of the city center that sustain the elevated surface and air temperatures, under hot, sunny and dryweather, during theMediterranean summer. A relationship between storage heat flux plus anthropogenic energy flux and temperatures (surface and lower atmosphere) is presented, that results in understanding of the interplay between temperatures, anthropogenic energy releases and the city characteristics under the Urban Heat Island conditions.