A new class of thermogelling poly(organophosphazenes) bearing a hydrophilic methoxypoly(ethylene glycol) (MPEG) and a hydrophobic tri or tetrapeptide such as GlyPheLeuEt, GlyPheIleEt, GlyLeuPheEt, and GlyPheLeuGlyEt have been synthesized and characterized by means of multinuclear (H-1, P-31) NMR spectroscopy, gel permeation chromatography, viscometry, and elemental analysis. The gelation of the present polymers is presumed to be attributed to the intermolecular interaction between the hydrophobic oligopeptide side groups, which can form strong physical junction zones in the polymer aqueous solution. The gelation properties of the polymer were affected by the subtle change in the nature of the hydrophobic oligopeptide, composition of the hydrophilic to hydrophobic side groups, and the concentration of the polymer solutions. Among the present thermogels, the copolymer with equimolar MPEG and GlyPheIleEt as side groups showed the excellent gel phase persisting over 35-43 degrees C, which indicates that it is a new promising material for drug delivery and tissue engineering. (c) 2005 Elsevier Ltd. All rights reserved.