Polyether dendrimers with differing chain end functionalites and molecular topologies were analyzed by MALDI-TOF mass spectrometry. The success of this analytical method is highly dependent on the type of matrix and sample preparation used. Ester and perdeuterophenyl terminated dendrimers with molecular weights up to 14,000 amu were successfully analyzed using an indoleacrylic acid matrix in tetrahydrofuran. Hybrid block copolymers consisting of linear polystyrene or poly (ethylene glycol) chains attached to one or two dendrimers gave spectra with oligomeric resolution in matrices of t-retinoic acid and 2-nitrophenyl octyl ether respectively. The MALDI-TOF results provide access to molecular weight distribution data confirming the results of size exclusion chromatography (SEC) analysis.