A new particle volume fraction measurement technique was developed using electron microscope analysis of thermophoretically sampled particles/aggregates based on a theoretical treatment of particle deposition to a cold surface immersed in a flame. This experimental method, referred to as the thermophoretic sampling particle diagnostic (TSPD), can yield all particle parameters of principal interest (particle volume fraction, particle and aggregate sizes, and fractal properties) without requiring knowledge of particle bulk density and refractive index. To assess its reliability, the TSPD technique was implemented at various heights on the centerline of a soot-containing coflowing ethylene/air nonpremixed laminar flame. Inferred soot volume fractions agreed with previous laser extinction and thermocouple particle densitometry measurements within experimental uncertainties at sampling positions where only aggregates of mature particles were present. However, TSPD-soot volume fractions were about a factor of 3 higher than light extinction results in the lower part of the flame. This significant difference was evidently a result of the presence of translucent precursor soot particles, which do not absorb as much visible light as mature particles, but can be quantified with the electron microscope. Clearly, this ability of TSPD to separately measure the concentration and morphology of each type of soot is a significant advantage over other available diagnostics, making it extremely valuable for studying particle formation in flames.