The Englishman, who sent off the Netherlands' John Heitinga as Spain won the 2010 tournament in extra time, is one of 25 referees heading to Brazil, including five South American officials, nine Europeans and three each from the CAF and CONCACAF zones.
In addition to the chosen 25, eight "support" referees will also be available at the event.
Webb is the only European official from 2010 making a return to the tournament, while Spain and Germany will be represented by Carlos Velasco Carballo and Felix Brych respectively.
France will be among the countries with no representation on the officiating roster.
Brazil's Sandro Meira Ricci has been handed the privilege of refereeing on home soil, and Marco Rodrguez of Mexico takes the whistle in his third World Cup.
Yuichi Nishimura of Japan is the only returning official among the Asian contingent, while Africa will be sending three World Cup debutants.
The competition gets under way on June 12, when hosts Brazil take on Croatia.
