Protoclusters, the progenitors of galaxy clusters, trace large scale structures in the early Universe and are important to our understanding of structure formation and galaxy evolution. To date, only a handful of protoclusters have been identified in the Epoch of Reionization. As one of the rarest populations in the early Universe, distant quasars that host active supermassive black holes are thought to reside in the most massive dark matter halos at that cosmic epoch and could thus potentially pinpoint some of the earliest protoclusters. In this Letter, we report the discovery of a massive protocluster around a luminous quasar at z = 6.63. This protocluster is anchored by the quasar and includes three [C II] emitters at z similar to 6.63, 12 spectroscopically confirmed Ly alpha emitters (LAEs) at 6.54 < z <= 6.64, and a large number of narrow-band-imaging selected LAE candidates at the same redshift. This structure has an overall overdensity of delta=3.3(-0.9)(+1.1) within similar to 35 x 74 cMpc(2) on the sky and an extreme overdensity of delta > 30 in its central region (i.e., R less than or similar to 2 cMpc). We estimate that this protocluster will collapse into a galaxy cluster with a mass of 6.9(-1.4)(+1.2)x10(15)M(circle dot) at the current epoch, more massive than the most massive clusters known in the local Universe such as Coma. In the quasar vicinity, we discover a double-peaked LAE, which implies that the quasar has a UV lifetime greater than 0.8 Myrs and has already ionized its surrounding intergalactic medium.