Russia are due to face Italy in Brindisi on April 23-24 but Myskina feels that her shoulder needs to be rested ahead of the French Open.
Myskina suffered a shock defeat to 15-year-old Czech sensation Nicole Vaidisova in the second round of the recent Family Circle Cup and does not want any further problems.
“We decided it was better not to take any more risks because we have Roland Garros coming up,” said Myskina's coach Jens Gerlach.
Russian Fed Cup captain Shamil Tarpischev has yet to name a replacement for Myskina, although world number 12 Nadia Petrova is the likely candidate to join Elena Dementieva, Elena Bovina and Dinara Safina in the squad.
