The pair will link up with Scarlets coach Pivac after the 2019 World Cup with current head coach Warren Gatland stepping down from his role after the tournament in Japan.
"I'm delighted with today's announcement. We are bringing in two hugely experienced, quality Welsh coaches to our set-up in Stephen and Jonathan," Pivac said in a statement.
"The WRU have been forward thinking with their planning and recruitment for post RWC 2019 and this has allowed me to bring in and secure the coaches we wanted."
Former flyhalf Jones made 104 appearances for Wales during a 13-year career before retiring in 2013. He joined Premiership side Wasps as an attack coach before linking up with Pivac at Scarlets as backs coach two years later.
Humphreys, who has 35 Wales caps, began his coaching career with Ospreys in 2005 before being named Scotland's forwards coach in 2013. After four years in the role, he moved to Glasgow to become the assistant coach at Warriors.
"Stephen and Jonathan are hugely respected not only for what they did on the field as players but in their careers as coaches and I'm delighted to have them as part of our team," Pivac said.
"They will bring a huge amount of experience, excitement and passion to their roles."
The WRU said skills coach Neil Jenkins and head of physical performance Paul Stridgeon would remain in their jobs. (Reporting by Shrivathsa Sridhar in Bengaluru; editing by Martyn Herman)
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