Mr Salmond is expected to be pressed on allegations of a "trade-off" with the Murdochs' newspapers, in return for support in last year's Holyrood elections.
He is also expected to be asked whether his own phone was hacked, after refusing to confirm or deny whether it had been targeted ahead of his appearance at the hearing.
As well as the grilling, the SNP leader is expected to set out his views on press regulation, an issue on which he has accused Westminster of a "systematic failure".
In recent weeks it has emerged that a number of high-profile Scottish politicians were victims of phone hacking. They include Joan McAlpine, now Mr Salmond's parliamentary aide.
The phones of former Labour First Minister Lord McConnell of Glenscorrodale and his children are also said to have been targeted.
Mr Salmond has repeatedly refused to say whether his mobile was hacked or not, insisting that the Leveson Inquiry into media ethics was the "appropriate forum" to answer the question.
The First Minister was dragged into the inquiry in April when he was namechecked in apparently explosive emails between Frederic Michel, a lobbyist for the Murdoch's News Corporation and James Murdoch.
They appeared to suggest Mr Salmond had agreed to lobby Culture Secretary Jeremy Hunt over News Corp's £8 billion BSkyB takeover bid. In one email, from February 11, 2011, Mr Michel wrote: "I met with Alex Salmond's adviser today. He will call Jeremy Hunt whenever we need him to."
Another email suggested Mr Salmond wanted Sky News to televise a debate between himself and Labour leader Iain Gray in the run-up to last year's Holyrood elections.
His office dismissed the emails, insisting they were merely "internal chatter" within the Murdoch empire.
However, Mr Salmond admitted he did want to argue in favour of the BSkyB Bid, because it would have been good for Scottish jobs.