Nicola Sturgeon is to meet the EU’s chief Brexit negotiator Michel Barnier in Brussels.
The meeting on Thursday morning comes as Mr Barnier prepares for the second round of negotiations between the UK and EU next week.
He will also hold talks with Labour leader Jeremy Corbyn and Carwyn Jones, the Welsh first minister.
But speaking on Wednesday, he stressed that Brexit negotiations would only be done with the UK government.
Mr Barnier said: “I have always made clear that I will listen to different points on view in the British debate.
“Of course, I will only negotiate with the UK government.”
He also called on the UK to offer more clarity on its position on the “divorce bill” financial settlement with the EU – which estimates have put at anywhere between €60bn to €100bn (£53bn to £89bn).
UK Foreign Secretary Boris Johnson told MPs earlier this week that the EU can “go whistle” for any “extortionate” final payment.
Mr Barnier said there were also major differences between the EU and UK on the rights of EU citizens living in Britain as well as on the “divorce bill”.
He said those issues – along with the nature of the future border with the Republic of Ireland – must be dealt with before future UK-EU trade could be discussed.
Ms Sturgeon, Scotland’s first minister, has consistently called for the Scottish government to have a “seat at the table” for the Brexit negotiations.
She has also called for a “short pause” in the Brexit process so consensus can be built across the UK on the best way forward.
The first minister wants membership of the European single market and the customs union to be at the heart of the process.
But Prime Minister Theresa May has insisted the UK will be leaving both.
The UK government has also previously rejected Ms Sturgeon’s calls for the Scottish government to be involved in the Brexit talks, and for Scotland to keep its single market membership even if the rest of the UK leaves.
But it has pledged to “consult” with the UK’s devolved administrations during the Brexit process.
Speaking ahead of Ms Sturgeon’s meeting with Mr Barnier, the Scottish Liberal Democrats urged her to push for an acknowledgment that Brexit can be cancelled and that the British people should have the final say on whatever deal is negotiated with the EU.