Charlotte was born in Schloss Ratiborschitz, Bohemia (now Ratibořice, Česká Skalice, Czech Republic), and grew up on the princely estate at Náchod.

Besides general cultural interests such as music and art she was also very keen on sporting pursuits such as swimming, tennis, cycling and - unusual for a woman of the time - skiing.

In 1890, William brought his new wife to England, where the Princess May of Teck commented, "We liked Charlotte very much, she is a good honest soul tho' rather too brusque, she seems to get on well with all the members of the Württemberg family which denotes great tact".

The principal reason appears to lie in Charlotte's perceived reluctance to carry out her public and ceremonial duties as it was felt she should have done.

She was also not thought regal enough for her new position; the Grand Duchess of Mecklenburg-Strelitz commented in 1892, "I heard ...that she is too jolly & off-hand for a Queen, and so ugly besides".

As convention demanded, she took over from her predecessor the patronage of a large number of social and charitable organisations, among them the body of deaconesses (Diakonissenwesen), the Swabian Women's Union (Schwäbische Frauenverein), the Württemberg Savings Bank (Württembergische Sparkasse) and the Red Cross.