Graphene has attracted signifi cant interest both for exploring fundamental
science and for a wide range of technological applications. Chemical vapor
deposition (CVD) is currently the only working approach to grow graphene at
wafer scale, which is required for industrial applications. Unfortunately, CVD
graphene is intrinsically polycrystalline, with pristine graphene grains stitched
together by disordered grain boundaries, which can be either a blessing or a
curse. On the one hand, grain boundaries are expected to degrade the electrical
and mechanical properties of polycrystalline graphene, rendering the
material undesirable for many applications. On the other hand, they exhibit
an increased chemical reactivity, suggesting their potential application to
sensing or as templates for synthesis of one-dimensional materials. Therefore,
it is important to gain a deeper understanding of the structure and properties
of graphene grain boundaries. Here, we review experimental progress
on identifi cation and electrical and chemical characterization of graphene
grain boundaries. We use numerical simulations and transport measurements
to demonstrate that electrical properties and chemical modifi cation
of graphene grain boundaries are strongly correlated. This not only provides
guidelines for the improvement of graphene devices, but also opens a new
research area of engineering graphene grain boundaries for highly sensitive
electro-biochemical devices.