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The purpose of this study is to improve the carbon monoxide (CO) and total hydrocarbons (THC) conversion efficiency of a diesel oxidation catalyst (DOC) by enhancing the monolith thermal behaviour through modification of the substrate cell density and wall thickness. The optimisation is based on catalyst properties (light off performance, conversion efficiency, pressure drop and mechanical durability). These properties were first estimated using theoretical equations derived from literature in order to select commercially available substrates for further modelling studies. The thermal behaviour and conversion efficiency of the selected catalysts under diesel exhaust gas conditions were numerically studied using data from an EU5 diesel engine operating a New European Driving Cycle (NEDC). This simulation was carried out on a commercial exhaust aftertreatment modelling program, AXISUITE. The predictions were compared to a reference coated 400/4 catalyst.