Tri-O-allylcellulose (degree of polymerization, DP similar to 112) was prepared in similar to 91% yield, and tri-O-crotylcellulose (DP similar to 138) was prepared in similar to 56% yield from microcrystalline cellulose (DP similar to 172, and polydispersity index, PDI similar to 1.95) using modified literature methods. Number-average molecular weight (M-n = 31,600), weight-average molecular weight (M-w = 191,800), and PDI = 6.07 data suggested that tri-O-allylcellulose may be crosslinking in air to generate branched chains. The polymer was stabilized with 100 ppm butylated hydroxy toluene (BHT). The material without BHT experienced glass transition (T-g, differential-scanning calorimetry, DSC) between -2 and +3 degrees C, crosslinked beyond 100 degrees C, and degraded at 298.6 degrees C (by thermogravimetric analysis, TGA). M-n (45,100), M-w (118,200), PDI (2.62), and thermal data (T-g - 5 to +3 degrees C, melting point 185.8 degrees C, recrystallization 168.9 degrees C, and degradation 343.6 degrees C) on tri-O-crotylcellulose suggested that the polymer was formed with about the same polydispersity as the starting material and is heat stable. While allylcellulose generated continuous flexible yellow films by solution casting, crotylcellulose precipitated from solution as brittle white flakes. Dynamic mechanical analysis (DMA) data on allylcellulose films (T-g - 29.1 degrees C, Young's modulus 5.81 x 10(8) Pa) suggest that the material is tough and flexible at room temperature. All H-1 and C-13 resonances in the NMR spectra were identified and assigned using the following methods: Double-quantum filter correlation spectroscopy (DQF COSY) was used to assign the network of seven protons in the anhydroglucose portion of the repeat unit. The proton assignments were verified and confirmed by total correlation spectroscopy (TOCSY). A combination of heteronuclear single-quantum coherence (HSQC) and C-13 spectroscopies were used to identify all bonded carbon-hydrogen pairs in the anhydroglucose portion of the repeat unit, and assign the carbon nuclei chemical shift values. Heteronuclear multiple bond correlation (HMBC) spectroscopy was used to connect the resonances of methines and methylenes at positions 2, 3, and 6 to the methylene resonances of the allyl ethers. TOCSY was used again to identify the fifteen H-1 resonances in the three pendant allyl groups. Finally, a combination of HSQC, HMBC, and C-13 spectroscopies were used to identify each carbon in the allyl pendants at 2, 3, and 6. Because of line broadening and signal overlap, we were unable to identify the conformational arrangement about the C5 and C6 bond in tri-O-allyl- and tri-O-crotylcelluloses.