A serial of novel star-shaped 2,4,6-trisubstituted 1,3,5-triazine (s-triazine) dendrimers were synthesized via step-by-step nucleophilic substitution starting from 2,4,6-trichloro-1,3,5-triazine, and were characterized by 1H, 13C NMR, FT-IR and ESI-MS spectra. The crystal structures for 2b, 2d and 4c have been determined by X-ray diffraction analysis, which indicate that there are hydrogen bonding and short contact interactions existing in intermolecules result in forming three-dimensional network architecture. D NMR experiments demonstrate that symmetrical trialkylamino-s-triazine shows correlated rotations of its N(2-ethoxy-2-oxoethyl) groups, while unsymmetrical 2-R-4,6-bis(dialkylamino)-s-triazines display two non-equivalent N(2-ethoxy-2-oxoethyl) groups, issued from the restricted rotation about the created C(s-triazine)-N bonds, and was conformed by crystallographic data.