The first apparition of the Blessed Virgin Mary would be in 40 AD when she appeared to St James the Greater. St James had traveled to Spain to convert those he encountered and became discouraged. During this time, Mary the mother God appeared to him and presented him with a small wooden statue of herself and a column of Jasper wood. The city was Zaragoza, Aragon Spain. The Basilica of Our Lady of the Pillar was built in Mary's honor as a result.
The Woman clothed in the sun, in Revelations chapter 12, is also believed to be the Blessed Virgin Mary.