Police deployed water cannon against some of the activists, who have threatened a permanent blockade of the motorway, vowing to "stay or come back every day" until fossil fuel subsidies are dropped.
Many protesters had come equipped with umbrellas and donned bathing suits or waterproof coats in preparation for the police water cannons.
Horns, whistles and police sirens could be heard around the city, as protesters paraded the streets in vehicles.
"A lot of money is being invested in the wrong place. Those using the most fossil fuels at the moment are the ones getting the most subsidies. This is slowing down the transition (to renewable energy)," Katrien Joosten, a 46-year-old architect told AFP, as she marched with her 13-year-old son.
"I can just about accept the water cannon, but I think he's too young to be arrested," she added, as she pulled him back from the front-line.
Around 25,000 people had turned out from across the country for the protest by early afternoon according to Extinction Rebellion.
The Hague mayoral spokesman Robin Middel put the turnout at 10,000-12,000.
Police made an unknown number of arrests.
Among those held was Dutch actress Carice van Houten, best known for her role as Melisandre in the hit TV series "Game of Thrones," said Extinction Rebellion spokeswoman Anne Kervers.
Police unions had warned in a statement on Friday that policing the demonstration required a deployment "that the Netherlands can ill-afford," with the protesters snarling traffic on a major entry route to The Hague.
The activists say the Dutch government hands around 37.5 billion euros ($40.2 billion) annually in subsidies to fossil fuel industries.
"No matter what The Hague city council makes the police do, we will stay or come back every day. And that's until the government meets our demand: an immediate end to all subsidies for fossil fuels", warned Extinction Rebellion Netherlands on its website.
At a similar event in May, police had also deployed water cannon to disperse the demonstration, arresting more than 1,500 people from a total of around 7,000 protesters.
The Extinction Rebellion (XR) group has conducted a series of high-profile stunts to draw attention to the climate change emergency, most recently targeting the US Open tennis semi-final in New York.
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