The Dutchman spent a year working at White Hart Lane, before moving to the Blues in controversial circumstances in 2005.
Arnesen spent time working for Hamburg after leaving Stamford Bridge in 2011 and has now penned a two-and-a-half year deal to become sporting director at Metalist.
"I'm glad to join Metalist," said Arnesen, who begins work on February 1.
"Thanks to the president Sergey Kurchenko for the opportunity. He has a very ambitious plan and I am sure that with this owner the club has a great future.
"The main goals that we set for ourselves is to win the Premier League of Ukraine and to perform in the Champions League."