Already trailing 3-0 after the first leg in Slovenia, Hibs never looked like staging a famous comeback after conceding the opening goal to visiting skipper Marcos Tavares after only 19 minutes.
Dutch midfielder Edwin de Graaf at least pulled the SPL outfit level on the night when he deflected in Anthony Stokes' shot shortly after the interval and also netted a late consolation in the closing seconds.
However, by then any faint hopes of progression had been dashed as Maribor restored their lead through Deja Mezga's penalty and extended it with Tavares' second of the night and third of the tie.
Hibs manager John Hughes brought defender Sol Bamba back in from the cold as he sought to piece together a side capable of pulling off a European night to remember.
The Ivory Coast international failed to turn up for pre-season training on schedule after being granted extra time off in the wake of the World Cup and was left out of the first leg in Slovenia and made to train with the youth team instead. However, Hughes recalled the former Dunfermline man to a team.
Hibs were well aware they required a good start and they made their Slovenian visitors endure an uncomfortable opening in a whirlwind first three minutes that lifted the home crowd.
And the Easter Road men might have found the early goal they craved with only six minutes on the clock.
Chris Hogg's header was missed by left-back Mitja Viler but Anthony Stokes neglected to shoot from his position on the right side of the box and the opportunity was gone.
Hibs had another chance six minutes later when Ian Murray's shot fell for de Graaf 12 yards out but the Dutchman's shot on the turn was too close to keeper Marko Pridigar.
Despite all their pressing the home side's task got even bigger with only 19 minutes gone.
Sinisa Andelkovic's corner from the right was met by Dejan Mezga and skipper Marcos Tavares claimed the final touch to leave Hibs needing five to progress.
The game was now realistically beyond them but Derek Riordan came close to giving the home fans something to shout about within three minutes of the start of the second half, only to see Pridigar beat away his 25-yard volley.
And they did then produce an equaliser on the night in the 54th minute.
Stokes turned inside onto his left foot on the edge of the box and his shot was deflected in by the body of De Graaf.
Nish then headed a Riordan cross wide from six yards out as the Edinburgh outfit attempted to at least earn victory on the night.
Stokes had a shot saved by Pridigar and then two efforts blocked before the home side conceded a 66th-minute penalty.
Mezga waltzed past Kevin McBride on the bye-line before going down under the Hibs midfielder's challenge from behind.
The midfielder picked himself up and calmly sent Smith the wrong way from the spot to restore the visitors' advantage.
And they moved further ahead with 17 minutes remaining courtesy of a lightning counter-attack.
Josip Ilicic crossed for Dalibor Volas on the break and his header back across the box was hammered high into the roof of the net by the excellent Tavares.
De Graaf repeated that feat in the 89th minute when Nish headed substitute David Wotherspoon's cross back to him 10 yards out but it was small consolation for the home side.