The 44-year-old has emerged as the favourite to take over from Delio Rossi after the Italian was sacked on Monday.
Sky Sport Italia reports that Mihajlovic met with Sampdoria directors on Wednesday and reached an agreement to become the club’s new coach. The contract will run until the end of the season with an option for a further year should he avoid relegation.
However he is still under contract with the Serbian association until June 2014, meaning a deal will not be complete until he reaches an agreement to have the contract broken.
Mihajlovic will meet with Serbian officials on Thursday, with Edy Reja the next name in line should the Serbian be unable to break his contract.
Follow Adriano Boin on Twitter: @Boin44