The first mass spectrometric analysis of a new class of hydrocarbon dendrimers that result from a convergent synthetic approach is reported. Molecular weights of a series of phenylacetylene dendrimers (715 to 14776 u MW) are characterized by ultraviolet matrix-assisted laser desorption (MALDltime-of-flight (TOF) mass spectrometry, direct and silver chemical ionization infrared laser desorption Fourier transform mass spectrometry @I'MSl, and ultraviolet matrix-assisted laser desorption silver chemical ionization Fourier transform mass spectromeby. New matrices and techniques were developed to facilitate analysis of the dendrimers. Mass measurement accuracies between 10 and 25 ppm are obtained for molecular ion species of the five dendrimers analyzed. Laser desorption time-of-flight and FI'MS techniques are shown to be complementary, with FTMS providing high mass resolution (27,000-67,000 resolving power) and accuracy for lower mass dendrimers (10-14 ppm) and MALD TOF yielding the highest resolution (1100 resolving power) and accuracy (25 ppm) for the largest dendrimer. These results are consistent with proposed empirical formulas.