Electronic states in 2D materials can exhibit pseudospin degrees of freedom, which allow for unique carrier-field interaction scenarios. Here, we investigate ultrafast sublattice pseudospin relaxation in graphene by means of polarization-resolved photoluminescence spectroscopy. Comparison with microscopic Boltzmann simulations allows to determine a lifetime of the optically aligned pseudospin distribution of $12pm 2,text{fs}$. This experimental approach extends the toolbox of graphene pseudospintronics, providing novel means to investigate pseudospin dynamics in active devices or under external fields.
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