Two days after Germany started their preparations in northern Italy, the Bayer Leverkusen player became the latest injury victim and pulled out of the 27-man provisional squad.
The 25-year-old, who has scored four times in 17 international appearances, picked up a "combined" muscle and tendon injury in his right thigh in training on Thursday evening and has already left the team camp.
"He left shortly before ten this morning after saying goodbye to the team," team spokesman Jens Grittner told reporters. "It had an effect on the atmosphere of the team."
"We wish Lars all the best for the coming days as he will undergo more tests and hope to have him soon with us again."
Bender's bad luck follows that of his twin brother Sven, who failed to make the squad because of injury, and throws the door open for unexpected call up Christoph Kramer of Borussia Moenchengladbach to claim a World Cup spot.
"When a player is ruled out so close before a tournament then it is very disappointing for everyone," Loew said. "I feel personally very sorry for Lars because I know how much he wanted to be in Brazil."
Bender is the latest German to suffer injury with captain Philipp Lahm and first choice keeper Manuel Neuer out for days and still to arrive in Italy because of knocks.
"They are expected to arrive this evening and join up with the team here," said Grittner.
Fellow Bayern Munich team mate Bastian Schweinsteiger is also yet to begin training with the team as he works on his fitness following a knee inflammation, while Real Madrid's Sami Khedira only recently returned to action from a cruciate ligament tear last year.
Top striker Miroslav Klose is racing to get fit in time of the tournament after an injury-plagued season at Italy's Lazio and has also yet to train with the team.
Several other players, including regulars Mario Gomez and Ilkay Guendogan did not even make the provisional squad after failing to return to full fitness from long injury absences this season.
The three-times World Cup winners have been drawn in Group G along with Portugal, United States and Ghana.
(Reporting by Karolos Grohmann, editing by Patrick Johnston and Pritha Sarkar)
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