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Knock occurrence is a widely recognized phenomenon to be controlled during the development and optimization of S.I. engines, since it bounds both compression ratio and spark advance, hence reducing the potential in gaining a lower fuel consumption. As a consequence, a clear understanding of the engine parameters affecting the onset of auto-ignition is mandatory for the engine setup. In view of the complexity of the phenomena, the use of combined experimental and numerical investigations is very promising. The paper reports such a combined activity, targeted at characterizing the combustion behavior of a small unit displacement two-stroke SI engine operated with either Gasoline or Natural Gas (CNG). In the paper, detailed multi-cycle 3D-CFD analyses, starting for preliminary 1D computed boundary conditions, are performed to accurately characterize the engine behavior in terms of scavenging efficiency and combustion.