The former top-ranked Russian will play the island's first Olympic champion in the inaugural Monica Puig Invitational in the capital city San Juan.
Sharapova, who last played an official match in January, said in a press release she was "excited to visit Puerto Rico for the first time and help Monica inaugurate her event."
She added: "Monica's Olympic story brought so much joy and pride to the people of Puerto Rico and I am happy to support her dream of playing tennis in her homeland."
Sharapova, 29, was suspended by the International Tennis Federation for failing a doping test in March. She said she had been taking the banned substance meldonium for health reasons but failed to notice it had been added to the banned list earlier this year.
She is set to return to the women's tour in April after the Court of Arbitration for Sport reduced her two-year sentence to 15 months in October, saying she bore "no significant fault or negligence."
Sharapova and Puig, both represented by management company IMG, have played each other only once with the Russian winning on the clay of Rome in 2014.
The day Puig faced Angelique Kerber for the tennis gold medal at the Rio Olympics, the streets in her native Puerto Rico were unusually calm.
Puerto Ricans were glued to their television sets as they watched the then 34th-ranked underdog stun the Australian Open champion from Germany to clinch the country's first ever gold medal.
In a US territory struggling with recession and a crippling debt crisis that has seen many leave, Puig's shock win offered a rare reason to celebrate.
After half a million people welcomed her home in August, Puig is giving something back: she's playing in her home country for the first time since 2011.
"Knowing that during the Olympics, the Island kind of 're-united' and people were, for a short while, able to forget the tough times and celebrate all together," Puig said in an email exchange last month. "I realized even more than before that I have a responsibility which I do not take lightly."
"I want to use my role, especially at home, to continue to bring happiness and success to Puerto Rico," added Puig, who was crowned best female athlete of the Rio Games by the Association of National Olympic Committees in November.
Although the 23-year-old Puig was born on the Caribbean island, she moved to Florida when she was a baby.
The Monica Puig Invitational will be held in Coliseo de Puerto Rico, the island's biggest indoor arena with a capacity of more than 16,000.
Puig said one level of the stadium will be used for people from public housing projects in San Juan, while she'll also host a kids' clinic with Sharapova.
Before Puig's victory, Puerto Rico had won eight Olympic medals. None of them were gold and they were all won by men.
Unusually, on the day of the Olympic women's tennis finals there were no reported murders in Puerto Rico, something the local police chief linked to the match.
Although tennis isn't widely played in Puerto Rico, Puig is hoping her success will give it a boost.
"I am very fortunate to be in the position that I am -- both in life and as an athlete," she said. "I want to bring tennis to Puerto Rico, help grow the sport, and have people enjoy and take pleasure out of this great sport and also for the next generation to be able to learn to play tennis, and use it as a tool to be successful in life."