Abstract We report the discovery of a 10 comoving megaparsec (cMpc)-scale structure traced by massive submillimeter galaxies (SMGs) at z ∼ 4.6. These galaxies are selected from an emission line search of ALMA Band 7 observations targeting 184 luminous submillimeter sources (S 850μm ≥ 6.2 mJy) across 1.6 degrees2 in the COSMOS field. We identify four [C ii] emitting SMGs and two probable [C ii] emitting SMG candidates at z = 4.60–4.64 with velocity-integrated signal-to-noise ratio of S/N > 8. Four of the six emitters are near-infrared blank SMGs. After excluding one SMG whose emission line is falling at the edge of the spectral window, all galaxies show clear velocity gradients along the major axes that are consistent with rotating gas disks. The estimated rotation velocities of the disks are 330–550 km s−1 and the inferred host dark-matter halo masses are ∼2–8 × 1012 M ⊙. From their estimated halo masses and [C ii] luminosity function, we suggest that these galaxies have a high (50%–100%) duty cycle and high (∼0.1) baryon conversion efficiency (SFR relative to baryon accretion rate), and that they contribute ≃2% to the total star formation rate density at z = 4.6. These SMGs are concentrated within just 0.3% of the full survey volume, suggesting they are strongly clustered. The extent of this structure and the individual halo masses suggest that these SMGs will likely evolve into members of a ∼1015 M ⊙ cluster at z = 0. This survey reveals a synchronized dusty starburst in massive halos at z > 4, which could be driven by mergers or fed by smooth gas accretion.