Webb, who showed 14 yellow cards and one red card in a bad-tempered Spain vs. Netherlands final in 2010, was selected from England ahead of Mark Clattenburg.
Each referee of the 25 referees was chosen with his regular team of two assistants. FIFA selected a further eight referees and eight assistants as reserves.
"The referees selected for the World Cup in Brazil have been chosen based especially on their personality and their quality in football understanding by being able to read the game and the teams' tactical approaches toward each game," FIFA said.
A former policeman, Webb was given control of the Sweden vs. Portugal playoff in Stockholm in November, when Cristiano Ronaldo scored a hat trick in a 3-2 victory.
Europe will provide nine of the 25 officiating teams, while South America has five, Asia has four, Africa and the CONCACAF region have three each and Oceania has one.
The youngest referee chosen is 33-year-old Wilmar Roldan of Colombia, and the oldest is 43-year-old Noumandiez Doue of Ivory Coast.
"FIFA has implemented a comprehensive program to ensure that the referees for its flagship competition are in peak condition," the governing body said in a statement.
A referee and his assistants can still be dropped from duty if they fail a fitness test before the opening match on June 12.
The World Cup officials are scheduled to attend a training camp next month and a seminar in Zurich in April.
Webb is among five of the 33 who were also selected for the 2010 World Cup in South Africa.
Others returning to the World Cup are Ravshan Irmatov of Uzbekistan, Yuichi Nishimura of Japan, Joel Aguilar of El Salvador and Peter O'Leary of New Zealand.
For the first time since 1974, there will be no French referee at the World Cup. Stephane Lannoy, who worked at the 2010 tournament, was on the original long list of candidates but was cut Wednesday.
2014 World Cup referees:
Asia: Ravshan Irmatov (Uzbekistan), Yuichi Nishimura (Japan), Nawaf Shukralla (Bahrain), Ben Williams (Australia)
Africa: Noumandiez Doue (Ivory Coast), Bakary Gassama (Gambia), Djamel Haimoudi (Algeria)
CONCACAF: Joel Aguilar (El Salvador), Mark Geiger (United States), Marco Rodriguez Moreno (Mexico)
South America: Enrique Osses (Chile), Nestor Pitana (Argentina), Wilmar Roldan (Colombia), Sandro Ricci (Brazil), Carlos Vera Rodriguez (Ecuador)
Oceania: Peter O'Leary (New Zealand)
Europe: Felix Brych (Germany), Cuneyt Cakir (Turkey), Jonas Eriksson (Sweden), Bjorn Kuipers (Netherlands), Milorad Mazic (Serbia), Pedro Proenca (Portugal), Nicola Rizzoli (Italy), Carlos Velasco Carballo (Spain), Howard Webb (England)