In the present contribution, investigations on the chemical modification of thermosetting melamine formaldehyde resins by natural polyol compounds are presented. As representative agents soluble starch, sucrose, and glycerol were chosen to cover three different classes of polyols. The major aim was to use substances produced from natural bio-renewable feedstock that are available in large quantities and may serve as environmentally innocuous and bio-renewable substitutes for petro-chemically derived and potentially hazardous materials. Different reaction conditions lead to resins with varying technical performance. For soluble starch no reaction conditions could be found that allow the adoption of this substitute for the laminate industry due to insufficient technological performance. Sucrose and glycerol on the other hand yielded impregnation resins with suitable performance. Chemical linkage of the modifying agent into the chain propagation by poly-condensation however, was only found with glycerol. The covalent incorporation of glycerol in the network was observed with addition of glycerol at different stages during synthesis. The technological performance of the various modified thermosetting resins was assessed by determining flow viscosity, molar mass distribution, the storage stability, and in a second step laminating impregnated paper to particle boards and testing the resulting surfaces according to standardized quality tests. Spectroscopic evidence of chemical incorporation of glycerol was found by applying by 1H, 13C, 1H/13C HSQC, 1H/13C HMBC, and 1H DOSY methods. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011