An effective method of producing small neutral carbon clusters Cn (n = 1-6) is described. The small carbon clusters (positive or negative charge or neutral) are formed by plasma which are produced by a high power 532nm pulse laser ablating the surface of the metal Mn rod to react with small hydrocarbons supplied by a pulse valve, then the neutral carbon clusters are extracted and photo-ionized by another laser (266nm or 355nm) in the ionization region of a linear time-of-flight mass spectrometer. The distributions of the initial neutral carbon clusters are analysed with the ionic species appeared in mass spectra. It is observed that the yield of small carbon clusters with the present method is about 10 times than that of the traditional widely used technology of laser vaporization of graphite.