Multilayer structures of W/C, WC/C, and Ru/C, of various periods were prepared and studied by high-resolution transmission electron microscopy. Comparison of the phases in the layered structures is made for as-prepared and annealed samples. Both as-prepared and annealed WC/C multilayers are predominantly amorphous, while the phases in the W/C depend on the periods. The 2 nm period W/C multilayer remains amorphous after annealing, and the longer periods recrystallize to form W2C. The layered microstructures of W/C and WC/C are stable on annealing at all periods, while the amorphous Ru-rich layers in the 2 nm period Ru/C multilayer agglomerate upon annealing to form elemental hexagonal Ru crystallites. Larger period Ru/C multilayers show stable layered structures, and indicate hexagonal Ru in the Ru-rich layers. X-ray measurements show that the multilayer periods expand on annealing for all metal-carbon multilayers studied.