The president is hoping to drum up international support as tensions grow between Spanish and Catalan authorities over the planned October 1 ballot.
Spain’s central government says the planned referendum violates Spain’s constitution, and the Constitutional Court has ordered it suspended while it studies its legality.
Mr Rajoy will visit the White House this Tuesday for the second time.
But as widespread unrest takes hold in his home country over the referendum, he aims to head to Washington this Monday and return to Spain by Wednesday.
The two leaders are set to meet over a working lunch and will hold a joint press conference in the Rose garden of The White House.
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It will be in direct contrast to the formal meeting that he had with then president of the country, Barack Obama in 2014, when they met for a formal meeting in the Oval office.
Thousands of Catalan separatists are rallying in public squares in Barcelona today and other towns in support of a disputed referendum on independence of the north-eastern region from Spain.
Catalonia represents a fifth of Spain’s 1.1 trillion-euro (£970 billion) economy and enjoys wide self-government.
The region has around 5.5 million eligible voters, and polls consistently show the region’s inhabitants favour a referendum but are roughly evenly divided over independence from Spain.
However, Mr Rajos, the leader of the Popular Party, hopes to rally support from America over the issue of Catalonia.
The US president appears to be putting precedence on his meeting with Mr Rajoy. Their meeting will take place a year since Mr Trump took office.
In addition, Mr Rajoy will not stay in a hotel, he has accepted Mr Trump’s invitation to stay at the Blair House with his delegation.
The building in front of the White House is used as an official residence for distinguished guests of the American president.
The meeting will be the first to be held between Mr Rajoy and Mr Trump after talking several times over the phone and greeting each other personally on two occasions during the NATO leaders’ meeting in Brussels in May and during the G20 summit in July in Hamburg.
The last time they both spoke was on the occasion of the August attacks in Catalonia when Trump called Mr Rajoy to convey his condolences and his solidarity.
In Catalan, separatists are pressing ahead vowing to declare independence if the “Yes” wins.