The 25-year-old was due to captain the European champions in their upcoming battles with the USA and the Czech Republic on Friday and next Tuesday respectively.
However, the FA confirmed earlier on Tuesday that Williamson was a doubt for the clash with the USA after sustaining an injury in training, and she has now been forced to withdraw entirely.
A statement from Arsenal revealed that the defender would undergo further assessment back home to determine the severity of the problem, and Lotte Wubben-Moy will replace her Gunners teammate in the Lionesses squad.
"We can confirm that Leah Williamson has withdrawn from the England squad after sustaining an injury in training. Leah will now return to Arsenal for further assessment," a statement read.
"Lotte Wubben-Moy has been called up to the squad to replace Leah and will link up with her England teammates today."
Sarina Wiegman has already lost Lucy Parker and Alessia Russo to injury as well as Williamson, and Nikita Parris has now joined the squad alongside Wubben-Moy.
Williamson's injury represents a second defensive blow in quick succession for Arsenal, who are set to be without Rafaelle Souza for several weeks after the Brazilian sustained a foot fracture against Ajax in the Champions League.
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