Police said a couple and their three children were travelling in Angra dos Reis, a popular coastal holiday destination about 90 miles from the city, when they drove into a crime-ridden slum by mistake.
A group approached the car and reportedly told the family to get out before opening fire, authorities said.
The woman was hit twice in the abdomen and was being treated at a hospital, police said. The victim underwent surgery and was in a stable condition, local media reported.
Police have not released any details of the family.
Bruno Gilaberte, local police chief, told O Globo newspaper that the family were looking for water at the time and had been told to head towards the area of Água Santa, or holy water.
"Because of the difficulty with the language, there was this confusion. They ended up going to the Holy Water community, where they were approached by the criminals. Because they did not understand the order to leave, they continued on and were shot," he said.
A Foreign Office spokesman said: "We are in touch with the local authorities in Angra dos Reis, Brazil, following reports of the shooting of a British national."
Tourists in Brazil have occasionally been attacked when they accidentally stray into slums, which are often controlled by criminal gangs.
The Foreign Office advises tourists to be wary of straying into favelas.
"All favelas are unpredictably dangerous areas, and remain high risk given the level of violence within them and the severe strain on police resources," its website says.
"Take extra care when using GPS navigation in Brazilian cities, particularly Rio de Janeiro, that the suggested route doesn’t take you into a favela."
Two years ago, a 70-year-old businesswoman was shot dead after using a mobile phone app which made her take a wrong turn into a favela in Rio de Janeiro.
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