The last-eight tie will be played at Fir Park on Sunday March 13, with a 12.30pm kick-off and shown live on BBC One Scotland.
Motherwell travelled to Easter Road at the same stage of the competition last season and after the two teams drew 2-2 in normal time and couldn’t be separated in extra time, Hibs won on penalties with centre-back Ryan Porteous smashing home the winning kick.
Hibs saw off Cove Rangers and Arbroath in the fourth and fifth rounds of this year's competition with ‘Well needing extra time to get past Morton before a more comfortable, normal-time victory over Aberdeen.
The two teams have met three times on league duty this season with Hibs winning 3-2 at Fir Park on the opening day of the season followed by a 1-1 draw at Easter Road and goalless stalemate in North Lanarkshire.
Hearts to sign new forward with Stephen Kingsley set to return
Predicted Hibs starting XI for Livingston clash - with post-derby decisions to make for Hibs boss
Hearts' European opponents confirmed as former Tynecastle winger prepares to return
Predicted Hearts XI for visit of Dundee United - with huge clash against Zurich in manager's mind
Zurich v Hearts live on TV as Europa League play-off tie is beamed back to Scotland