We have demonstrated for the first time the application of a small angle neutron scattering (SANS) technique for the precise determination of the onset of hydrocarbon transport (primary migration) in shaly source rocks. We used a sequence of rocks pyrolysed in the laboratory under nitrogen at temperatures in the range 310-370°C. These rocks contained several percent of dispersed marine Type II organic matter. Geochemical analysis indicated a peak of the hydrocarbon generation in the middle of the temperature range (at 340°C). We observed a sharp decrease of SANS intensity in a narrow maturity range within the geochemically determined region of the onset of hydrocarbon generation. This decrease was a direct consequence of the SANS contrast variation caused by the invasion of the pore space by bitumen during the primary migration of hydrocarbons. A similar phenomenon was observed for a natural maturity sequence of source rocks originating from the same location.