The Nb3Sn-based bronze-processed multifilamentary composites have been fabricated at the Bochvar Institute of Inorganic Materials, Moscow, Russia, and studied by electron microscopy to determine the relationships between their structural parameters and annealing duration at different temperatures (575 °C, 650 °C, 750 °C). The structure of superconducting layers during their formation is characterized by thickness, average size of equiaxed grains, and by the fraction ratio of columnar and equiaxed grains. It was found that at high diffusion annealing temperatures (above 650 °C), the superconducting layers grow much faster, but the average size of equiaxed Nb3Sn grains even under a short exposure (10 h) is much larger than after a long low-temperature annealing. It is shown that to ensure the best current-carrying capacity of Nb3Sn-based wires in high magnetic fields, it is necessary to take into account different trends: on the one hand, the possibility of approaching the Nb3Sn phase stoichiometry and providing its maximum amount and on the other hand to avoid the undesirable growth of grains resulting in a lower pinning force.