The wide use of biodiesel has been driven by its reduction potential on greenhouse emissions from diesel engines without significant technological modifications. In this study a diesel engine for non-road applications has been fuelled with Waste Cooking Oil biodiesel blended with commercial fossil fuel at 6% and 30% v/v. In line with literature trends, experimental results indicate a significant reduction of PM emissions and only a slight increase in NOx emissions. This study has been focused on diesel emissions and in particular on the analysis of PM/NO2 ratio in presence of the Diesel Oxidation Catalyst (DOC). In fact, although the NO2/NOx ratio on raw exhaust is almost unaffected, the use of biodiesel shows a slight reduction of the NO-NO2 light-off temperature. This reduction can ensure more favorable operating conditions for the Diesel Particulate Filter (DPF), and has a positive effect on fuel consumption reduction. In order to deeply analyze these issues, a numerical model of an Aftertreatment system (AS) representing the a DOC and a DPF has been developed and validated with experimental data.