Pampinea is the de facto leader of the brigata, the group of young Florentines who escape their plague-ridden city and tell each other stories in an isolated villa. Leaving the city is Pampinea’s idea, setting the tone for her leadership as the other characters demure to her role as a leader. In her late twenties, she is the oldest member of the group and she shows her authority by becoming the queen for the first day. The ideas and structures she introduces as queen (such as the selection of a theme and the way in which the king or queen select the next storyteller) are broadly copied by everyone else. Whereas other members of the group may be bawdy, shy, or emotional, Pampinea retains control of her emotions at all times. Her calm authority is a demonstration of her maturity and this maturity allows the others to trust Pampinea as their leader.

When speaking between the stories, Pampinea hints that her maturity may be affected by a tragic understanding of love. She claims to have been in love many times but she never explicitly mentions a current romantic partner. Likewise, she is almost a decade older than most of the characters in the stories who are described as being of a marriageable age.