Pietersen, 35, was the first Platinum Pick for Quetta Gladiators, while England all-rounder Chris Jordan was chosen by Peshawar Zalmi.
Pakistan bowler Mohammad Amir, back from a five-year ban for spot-fixing, will play for Karachi Kings alongside England batsman James Vince.
The tournament will take place in February in Dubai and Sharjah.
Luke Wright was also selected by Quetta, while fellow England all-rounder Ravi Bopara features in Karachi's squad.
West Indies opener Chris Gayle and Australia all-rounder Shane Watson were the first picks for Lahore Qalandars and Islamabad United respectively.
Now a freelance Twenty20 specialist, Pietersen struck successive centuries as he helped his Dolphins franchise reach the final of the Ram Slam, South Africa's domestic T20 competition, this month.
Currently playing in the Australian Big Bash, he hit 76 from 42 balls for Melbourne Stars on Saturday.
Teams finished with nine players after day one of the draft in Lahore.
They will complete their squads - of between 16 and 20 players - when they select from the Silver and Emerging categories on the second day.
Peshawar Zalmi: Shahid Afridi, Wahab Riaz, Darren Sammy, Kamran Akmal, Mohammad Hafeez, Chris Jordan, Tamim Iqbal, Junaid Khan, James Allenby.
Karachi Kings: Shoaib Malik, Shakib Al Hasan, Sohail Tanvir, Imad Wasim, Ravi Bopara, Lendl Simmons, Mohammad Amir, Bilawal Bhatti, James Vince.
Islamabad United: Shane Watson, Andre Russell, Misbah-ul-Haq, Samuel Badree, Mohammad Irfan, Brad Haddin, Sharjeel Khan, Mohammad Sami, Khalid Latif.
Quetta Gladiators: Kevin Pietersen, Sarfraz Ahmed, Ahmed Shehzad, Anwar Ali, Jason Holder, Luke Wright, Zulfiqar Babar, Umar Gul, Elton Chigumbura.
Lahore Qalandars: Chris Gayle, Dwayne Bravo, Umar Akmal, Mohammad Rizwan, Yasir Shah, Sohaib Maqsood, Mustifzur Rehman, Kevon Cooper, Cameron Delport.
Former England batsman Kevin Pietersen was selected in the player draft for the inaugural Pakistan Super League.