Combustion-generated soot particles can have significant impact on climate, environment and human health. Thus, understanding the processes governing the formation of soot particles in combustion is a topic of ongoing research. In this study, high-resolution atomic force microscopy (AFM) was used for direct imaging of the building blocks forming the particles in the early stages of soot formation. Incipient soot particles were collected right after the particle nucleation zone of a slightly sooting ethylene/air laminar premixed flame at atmospheric pressure and analyzed by AFM after a rapid sublimation procedure. Our data shed light on one of the most complex and still debated aspect on soot formation, i.e., the nucleation process. The molecular constituents of the initial particles have been individually analyzed in detail in their chemical/structural characteristics. Our data demonstrate the large complexity/variety of the aromatic compounds which are the building blocks of the initial soot particles. Nevertheless, some fundamental and specific characteristics have been clearly ascertained. These include a significant presence of penta-rings as opposed to the purely benzenoid aromatic compounds and the noticeable presence of aliphatic side-chains. In addition, there were indications for the presence of persistent π radicals. Incipient soot was also investigated by Raman spectroscopy, the results of which agreed in terms of chemical and structural composition of the particles with those obtained by AFM.