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Unusually small carbon nanoparticles were synthesized in a microwave plasma flow-reactor by pyrolysis of 0.3–1.2% CH4, C2H4, and C2H2 with 0.3–3.6% addition of molecular hydrogen in argon. Final particle sizes were analyzed by in-line particle-mass spectrometry (PMS) and by transmission electron microscopy (TEM). TEM measurements of primary particle sizes were found to be in a good agreement with PMS data. The carbon particles formed in the plasma generated by a 2.45 GHz magnetron with an applied power of 180 W and a total pressure of 13 mbar have diameters of 4–6 nm. The type of hydrocarbon precursor and 0.3–3.6% of hydrogen addition did not noticeably influence the final particle sizes. The formation of such small particles is attributed to the low pressure and the comparably low operation power. This method of small carbon nanoparticles synthesis could be useful for the production of carbon black material, where large surface area is important.