The 38-year old will, once again be competing in the cross-country skiing events, as she did at Turin 2006 and Vancouver 2010. However, having added marksmanship to her sporting repertoire, she will also become the first ever Brazilian athlete to compete in the biathlon.
And as if that were not impressive enough, Mourão has also represented Brazil as a mountain biker at both Athens 2004 and Beijing 2008.
She first turned her hand to the biathlon after Vancouver 2010 when she was also pregnant with her son, who is now three.
"It was a big thing to be a mum and to start a new sport," she says with just a touch of understatement.
Brazil does not perhaps benefit from the ideal climactic or geographical conditions for preparing for a biathlon, and Mourão acknowledges the invaluable role played by the IOC’s Olympic Solidarity programme in her preparations for Sochi 2014
With the help of the Olympic Solidarity programme, we’ve had a training programme of the highest quality,” she explains. “Along with the physical tests, my shooting practice has shown a considerable improvement.”
Not many athletes manage to straddle Summer and Winter Games, but Mourão believes that the two have much in common. “The structure of the Village, the organisation, the security, the competition format in general is very similar, though the Summer Games have more athletes, more countries and more heat!”
“On the other hand,” she adds, “the Winter Games are more charming because of the snow and the interaction between the athletes, which is bigger as we stay longer at the venues.”
However, there is one common denominator that continues to drive and inspire Mourão, and that is the pride she takes from being an Olympian and flying the Brazilian flag: “In the end, each edition of the Olympic Games is unique, and to represent my country for the fifth time would be a huge honour,” she adds