The move comes as EU leaders agree to extend a border aid mission in Libya and restrict sales of inflatable boats to stem the ongoing crisis.
Every day ships packed with migrants are flooding into European waters.
So far this year more than 85,000 people have made it to the shores of Italy.
But a ship crewed by anti-Islam and anti-migrant activists from France, Germany, Austria and Italy is taking to the Mediterranean on a mission to flout European law and send refugees back to Libya.
"Every week, every day, every hour ships packed with illegal immigrants are flooding the European border. An invasion is taking place. (Male 2) This mass immigration is changing the face of our continent. We're losing our safety, our way of life and we will become a minority in our own country. Our future is under attack."
The 'Defend Europe' group crowdfunded more than $100,000 to pay for its mission, which one of its backers says was partly inspired by an Australian government anti-immigration ad campaign.
Activist Martin Sellner says they will monitor the actions of NGO rescue ships and return migrants from their boats back to Africa.
"As soon as we arrive there we will oversee the NGOs, record all of the radio signals, expose possible communication with the human traffickers and intervene when they are doing something illegal. We will cooperate with the Libyan coastguard and inform them every time when an NGO ship tries to enter Libyan waters and we will try to sink all the abandoned migrant and trafficker ships in order to prevent the human traffickers from getting them back in the night and thus draining their financial resources."
The group's move comes just days after Italy introduced a controversial code of conduct for NGOs working in the Mediterranean.
Among Italy's new rules is a ban on making phone calls or firing flares, which the Italian government claims could signal to human traffickers when it is safe to send a boat to sea.
But, the UK-based organisation Hope Not Hate says, the far-right Defend Europe organisation threatens to hinder the lifesaving work of search-and-rescue NGO ships in the area.
During the first four months of 2017, more than one-third of rescue operations in the Mediterranean were carried out by NGOs and private rescue teams.
Libyan coastguard commander BuIjaya Abdelbary says his crew are trying to stop people making the dangerous journey but they are not getting the help the EU has promised.
"We've contacted the European Union and explained our needs to help us capture the smugglers and to help with our search and rescue operations. They understand our situation but we have yet to see them deliver on their promises."
The migration crisis has been the centre of talks between European foreign ministers and representatives from the UNHCR and the International Organisation for Migration in Brussels.
Foreign ministers have agreed to extend a border aid mission in Libya until the end of 2018 that helps Libyan security forces, notably in the lawless south.
European Union Foreign Policy Chief Federica Mogherini says the EU also decided to allow members to restrict sales of inflatable boats and outboard motors to Libya in an effort to stop dangerous migrant smuggling across the Mediterranean.
"We also took a decision to introduce restrictions today, from today onwards, on the export and supply to Libya of the inflatable boats and motors. As you know, these are devices that are used by traffickers for their smuggling activities, so this decision we have taken on the European Union level will help making their businesses and their lives a bit more complicated, even more, actually, I would say."
The Director General of the International Organisation for Migration, William Lacy Swing, says international organisations are collectively working to find a comprehensive solution.
"Obviously we are particularly concerned about the number of deaths that continue to occur, we are working on that now, and this really depends a lot on trying to bring stability back to Libya and that part of the world where so many of the migrants are coming from."
More than 2,000 refugees and migrants have died in the central Mediterranean since January this year.
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