Characterization of amino-terminated polyamidoamine dendrimers by CE suffers from a lack of resolution for higher generations and poor between-day reproducibility of retention times. Under optimal conditions of temperature, voltage, and sample amount, 0-5 generations of dendrimers could be resolved with a bare fused-silica capillary. However, reproducibility was poor due to potential interactions of the polycationic dendrimers with the uncoated quartz capillary wall. Use of a poly(vinyl alcohol)-coated capillary significantly decreased the migration times of the nanomolecules without compromising resolution. Dendrimer mixtures containing generations 0-5 are separated as discrete, nonoverlapping peaks in about 15 min. In addition, the between-day precision of retention times was dramatically improved without the need for internal standards or data normalization. Dendrimers of various generations and cores run on different days showed an RSD of retention times of less than 4%. The poly(vinyl alcohol) coating was very stable as shown by the excellent precision of migration times obtained on a capillary used for a month with more than 100 injections. Similar to PAGE, separation of polyamidoamine dendrimers on a bare fused-silica and poly(vinyl alcohol)-coated capillary showed an exponential relationship between migration times and calculated charge density of the nanomolecules.