Graphene grown by chemical vapor deposition (CVD) is the most promising material for industrial-scale applications based on graphene monolayers. It also holds promise for spintronics; despite being polycrystalline, spin transport in CVD graphene has been measured over lengths up to 30 µm, which is on par with the best measurements made in single-crystal graphene. These results suggest that grain boundaries (GBs) in CVD graphene, while impeding charge transport, may have little effect on spin transport. However, to date very little is known about the true impact of disordered networks of GBs on spin relaxation. Here, by using first-principles simulations, we derive an effective tight-binding model of graphene GBs in the presence of spin-orbit coupling (SOC), which we then use to evaluate spin transport in realistic morphologies of polycrystalline graphene. The spin diffusion length is found to be independent of the grain size, and is determined only by the strength of the substrate-induced SOC. This result is consistent with the D'yakonov-Perel' mechanism of spin relaxation in the diffusive regime, but we find that it also holds in the presence of quantum interference. These results clarify the role played by GBs and demonstrate that the average grain size does not dictate the upper limit for spin transport in CVD-grown graphene, a result of fundamental importance for optimizing large-scale graphene-based spintronic devices.The growth of graphene via chemical vapor deposition (CVD) is the most promising approach for realizing industrial-scale applications of this material 1 . One drawback of CVD-grown graphene is that it tends to be polycrystalline, with misoriented single-crystal domains separated by grain boundaries (GBs) consisting of arrays of five-, seven-, and occasionally eight-member carbon rings. In some specific cases the GBs can be characterized by a given periodicity, but more generally they tend to be complex meandering arrangements of these nonhexagonal rings 2,3 . Charge transport and scanning tunneling measurements have revealed that graphene GBs serve as a significant source of charge scattering, leading to enhanced resistance 4,5 and localization effects 4,6,7 . Only when the graphene grains become larger than 1-10 µm do the GBs cease to dominate the charge transport in CVD graphene 8 .Graphene also has clear advantages for spintronic applications, owing to its low intrinsic spin-orbit coupling (SOC) 9-11 . Combined with its high electron mobility, this can lead to spin diffusion lengths as long as 30 µm in clean exfoliated graphene-based devices (with mobility up to several 10, 000 cm 2 /V-s) 12 . Intriguingly, spin diffusion lengths as long as 10 µm and spin currents measurable over channel lengths of 30 µm have also been reported in disordered CVD graphene with much lower charge mobility 13,14 . These measurements can be explained in two different ways: either none or very few GBs were present in the measured devices; or GBs in CVD graphene, while impeding charge transport, have little effect ...