Biodiesel and blends with petroleum diesel are promising renewable alternative fuels for engines. In the present study, the soot concentration generated from four biodiesels, two pure methyl esters, and their blends with petroleum diesel are measured in a series of fully pre-vapourised co-flow diffusion flames. The experimental measurements are conducted using planar laser induced-incandescence (LII) and laser extinction optical methods. The results show that the maximum local soot volume fractions of neat biodiesels are 24.4% - 41.2% of pure diesel, whereas the mean soot volume fraction of neat biodiesel cases was measured as 11.3% - 21.3% of pure diesel. The addition of biodiesel to diesel not only reduces the number of inception particles, but also inhibits their surface growth. The discretised population balance modelling of a complete set of soot processes is employed to compute the 2D soot volume fraction and size distribution across the tested flames. The results show that the model also demonstrates a reduction of both soot volume fraction and primary particle size by adding biodiesel fuels. However, it is not possible to clearly determine which factors are responsible for the reduction from the comparison alone. Moreover, analysis of the discrepancies between numerical and experimental results for diesel and low-blending cases offers an insight for the refinement of soot formation modelling of combustion with large-molecule fuels.