SnO2–graphite nanocomposites are prepared by urea-mediated homogeneous hydrolysis of SnCl4. Heating in a CEM Discover microwave reactor (Sn–C-1), in a household microwave oven (Sn–C-2), or by a conventional conduction method (Sn–C-3) are used to decompose the urea and release hydroxide ions for SnCl4 hydrolysis. The nanocomposites are characterized by XRD, ICP, FE-SEM, SEM and TEM/SAED and used as the material for negative electrodes (anodes) in Li-ion batteries. The SnO2 particles in Sn–C-1 are the smallest and have the narrowest size distribution (1–3nm, mean: 2.1nm, standard deviation: 0.3nm) compared with those in Sn–C-2 (2–5nm, mean: 3.8nm, standard deviation: 0.5nm) and Sn–C-3 (3–9nm, mean: 6.4nm, standard deviation: 0.9nm). The microwave preparation allows smaller SnO2 particles to be produced and more homogenously dispersed in the graphite. This results in improved electrochemical performance as a lithium storage compound. The specific capacities decrease in the order: Sn–C-1>Sn–C-2>Sn–C-3. For the 14.2wt.% SnO2–graphite composite (Sn–C-1), the initial specific capacity was 465mAhg−1 and 80% of the initial specific capacity, or 372mAhg−1 can still be obtained after 60 charge and discharge cycles.