The singer announced that the collaborations will feature on each of their respective new albums, which are due out later this year.
"Now headed to a COVER SHOOT with big bro @UsherRaymondIV - we got duets on both of our albums coming," Bieber tweeted.
Usher later added: "Proud of @justinbieber for his new single #BOYFRIEND - the biggest selling worldwide single first week EVER!
"Ohh (sic)… and trust we got a duet coming for "LOOKING 4 MYSELF" and "BELIEVE" he has come a long way. Proud to see his evolution as an artist!"
Usher will release his seventh studio album Looking For Myself on June 11 in the UK and June 12 in the US.
Justin Bieber's third studio set Believe is expected to follow later in the year.
> Justin Bieber channels Michael Jackson in new video teaser - watch
Listen to Justin Bieber's new single 'Boyfriend' below: