Despite intensive research efforts over the past 3 decades, the structural analysis of sulfur-vulcanized natural rubber (NR) remains challenging owing to the complexity and low population of its sulfur moieties. Herein, solid vulcanized NR samples and NR samples reacted with sulfur and other reactants in an organic solvent were analyzed by solid-state NMR with fast magic-angle spinning and solution NMR, respectively. The present high-field two-dimensional NMR analysis revealed six novel sulfur moieties in these samples, including cyclic sulfides, cyclic di/polysulfides, and crosslinked structures with a vinylidene group. While previous studies reported a variety of sulfur-crosslinked structures in NR, our analysis identified only two dominant types of crosslinked structures that matched those reported previously. Our NMR assignments for the crosslinked structures were inconsistent to a large extent with those presented in the previous studies; thus, in the current work, the crosslinked structures were reassigned using the new data. Based on quantitative NMR analysis, this study also provides the first tangible evidence that cyclic rather than crosslinked sulfides can be the dominant sulfur moieties in vulcanized NR. These results may drastically alter the previously established structural landscape of sulfur-vulcanized NR.