This paper presents the details of a Computational Fluid Dynamics methodology to accurately model the process of mixture preparation in modern Gasoline Direct Injection engines, with particular emphasis on liquid film as one of the main causes of Particulate Matter formation. The proposed modelling protocol, centred on the Bai-Onera approach of droplets-wall interaction and on multi-component surrogate fuel blend models, is validated against relevant published data and then applied to a modern small-capacity GDI engine, featuring centrally-mounted spray-guided injection system. The work covers a range of part-load, stoichiometric and theoretically-homogeneous operating conditions, for which experimental engine data and engine-out Particle Number measurements were available. The results, based on the parametric variation of start of injection timing and injection pressure, demonstrate how both fuel mal-distribution and liquid film retained at spark timing, may contribute to PN emissions, whilst their relative importance vary depending on operating conditions and engine control strategy. Control of PN emissions and compliance with future, more stringent regulations remain large challenges for the engine industry. Renewed and disruptive approaches, which also consider the sustainability of the sector, appear to be essential. This work, developed using Siemens Simcenter CFD software as part of the Ford-led APC6 DYNAMO project, aims to contribute to the development of a reliable and cost-effective digital toolset, which supports engine development and diagnostics through a more fundamental assessment of engine operation and emissions formation.