The magic circle giant would not comment on its role but it is understood that London-based corporate partners Richard Godden and James Inglis are playing a key part in the Linklaters team.
Rio Tinto rejected the initial approach by BHP but it is understood that the group is likely to launch a fresh bid in the coming weeks, with many analysts predicting the approach would become hostile if necessary.
BHP has turned to long-term adviser Slaughters, for whom high-profile corporate veteran Nigel Boardman is the relationship partner.
The latest bid comes with the mining sector having generated a slew of major M&A deals over the last couple of years, with Linklaters among the beneficiaries.
Earlier this year, the City giant advised Rio Tinto on its tie-up with Canadian metal group Alcan – a deal that was worth around $34bn (£16.8bn).
Godden led the Linklaters team on that deal, with fellow partners Inglis, Gavin Robert (competition) and Stuart Thomas (banking and finance) all playing roles.
Freshfields Bruckhaus Deringer competition partners John Davies and Alan Ryan are advising Alcan in the negotiations on European Union competition law, with Sullivan & Cromwell reportedly bagging a role in the