Jacques Barrot, the European transport commissioner, described some of their planes as "flying coffins" and said safety controls were too weak.
None of the airlines on the 92-strong blacklist currently operates in Britain and most are already barred by the government.
African carriers account for the lion's share of the list, along with others from Afghanistan, North Korea, Thailand, Kazakhstan and Kyrgyzstan. It includes 50 airlines from the Democratic Republic of Congo, 14 from Sierra Leone, 11 from Equatorial Guinea, seven from Swaziland and three from Liberia.
Lesser restrictions were placed on Air Bangladesh and Buraq Air from Libya, which will be able to operate flights if they use leased planes that meet safety requirements.
The list, which was drawn up following a spate of accidents, is a pre-emptive strike because few of the airlines operate in Europe.
Mr Barrot, who announced the 25-nation-wide ban, said: "This blacklist will keep dubious airlines out of Europe. It will also make sure that all airlines operating in Europe's sky meet the highest safety standards."
However, it advised passengers to avoid travelling with the airlines elsewhere in the world.
Tour operators will be required to inform passengers of the identity of the airline. Under the new rules, passengers will also have a right to compensation if the airline on which they were to fly was included on the blacklist or replaced by a blacklisted airline after they bought the ticket.
The list, which will be reviewed every three months, was compiled from those held by individual EU member states.