Alexandra's marriage to the future Edward VII in 1863 made her Princess of Wales and began decades of public appearances on behalf of the monarchy. She opened bazaars, attended concerts and visited hospitals, sometimes undertaking engagements for Queen Victoria. Her interest in the London Hospital and in care for wounded servicemen became recurring features of her work.

She became queen consort in 1901 and was crowned with Edward in August 1902 after his illness postponed the ceremony. That year the War Office established Queen Alexandra's Imperial Military Nursing Service by royal warrant, with Alexandra as its president. Her support for nursing connected royal patronage with an increasingly organized professional service. She also encouraged fundraising for medical care during Britain's overseas campaigns.

An amateur photographer, Alexandra used her own pictures for charitable publication. Her Christmas Gift Book of 1908 reproduced 136 snapshots and sold in Britain, America and other countries, benefiting more than thirty charities. After Edward's death in 1910 she continued public work as queen mother. In 1912 she launched Alexandra Rose Day, drawing on a Danish model of selling artificial roses. Volunteers sold silk flowers to raise money so hospitals could treat people unable to afford care. The annual appeal extended her charitable activity beyond court events into street collections. She spent much of her later life at Sandringham and died in 1925.