From Saturday, citizens of the three former Yugoslav republics who hold biometric passports will not need visas to enter the borderless Schengen area.
The visa waiver follows measures by the three would-be EU members to beef up border security and tackle crime.
The UK still requires visas, because it is outside the Schengen agreement.
As Yugoslavia began its slow and painful collapse in the early 1990s, visa restrictions were imposed on all citizens to stem the tide of refugees fleeing the fighting, says the BBC's Balkans correspondent, Mark Lowen.
Slovenia and Croatia gained visa-free travel shortly after their independence in 1991, but for the other republics, the regulations remained in place.
And the impact is still felt, says our correspondent: 70% of Serbs don't even own passports, discouraged from travelling by the cost and time of applying for visas.
Path to integration
Serbia's President Boris Tadic has described the move as "a practical and clear step towards European integration".
The visa waiver does not apply to Kosovo, whose independence from Serbia is not recognised by all EU member states.
The Schengen zone is made up of 25 European countries - the 27 EU members, minus the UK, Ireland, Bulgaria, Romania and Cyprus; plus three non-EU nations - Norway, Iceland and Switzerland.
Although Bulgaria and Romania are not yet in Schengen they do have visa-free arrangements with the EU, so they will also ease the travel rules for their Balkan neighbours, if they have not already done so unilaterally.
The EU governments said Albania and Bosnia-Hercegovina had not yet met all the benchmarks required for visa liberalisation.
Brussels says both countries need to speed up necessary reforms in order to be granted the measure - leading to some criticism that they may be left further behind their neighbours as this region edges slowly further on its path to Europe, says our correspondent.
Macedonia has been a candidate for EU membership since 2005, but its accession is being held up by a dispute with neighbouring Greece over the country's name.
Serbia's pro-Western government has been told its EU accession depends on the capture of the last two remaining major war crimes suspects, former Bosnian Serb army chief Gen Ratko Mladic and the former Croatian Serb leader, Goran Hadzic.
This comment really was so worthy of our politics and were it has left our people! This is when politician's respect their own people. It is almost the same psychology as a household, that if you do not respect and love your household members, why should the others care! But hey we have kept the stability in Balkans, and the others get the piece of the cake.
Dear fellow Albanians,
How does it feel to be last in everything in the past 19 yrs. How does it feel when a nation the size of tirona(pop), an artificial state barely hanging together(FYROM also candidate state), and a butcher state responsible for killing 200,000 bosnians and 13,000+ Albanians, is hardcore pro Russia and surpassed Albania when it came to closer ties with the EU.......