This paper is concerned with the formation of Particulate Matter (PM) in direct-injection (DI) diesel engines. A system featuring an electromagnetically actuated sampling valve was used for sampling of gas directly from the combustion chamber. The concentrations of total particulate matter (TPM) and of its two components, the Soluble Organic Fractions (SOF) and the Insoluble Fractions (ISF), were determined at different locations in the combustion chamber at different sampling times (different crank angles). High concentrations of SOF were found at sampling positions along the spray flame axis. The concentrations of SOF and ISF were higher at sampling positions close to the wall than away from the wall. The results suggest that SOF formation is significantly affected by wall quenching. Also, the PM concentrations were much higher in the combustion chamber than in the exhaust.