Both teams were playing for pride having been eliminated from the finals race but it was a pulsating match throughout with Karlitzek scoring four of his 13 points in the decider to propel Germany to a 3-2 (21-25, 25-22, 23-25, 25-23, 15-13) triumph.
Five German players reached double figures led by Moritz Reichert (17 points) and Simon Hirsch (16), while a brave Bulgaria ran out of puff but veteran Boyan Yordanov tried hard with 15 points.
With identical 5-7 records coming into the contest, both teams had a faint hope of qualifying for next month's finals in Lille but it quickly evaporated due to other results.
It meant both coaches could test their depth with Germany deciding to rest captain Christian Fromm and star Tobias Krick, while Nikolay Uchikov sat for the first three sets for Bulgaria.
Bulgaria were looking for their third straight victory after finding form at home during the fourth phase but were halted by 21-year-old Karlitzek, who showed maturity beyond his years with a commanding fifth set display filled with poise and skill.
It was a disappointing result for Bulgaria after a bright start with Svetoslav Gotsev, their third highest scorer of the VNL, hammering home an imposing spike followed by a monster block from Georgi Seganov.
Bulgaria appeared likely to skip away to an early lead but the towering presence of Hirsch ensured Germany kept pace as - indicative of the standings - little separated the teams. Both teams were struggling to hold serve as points were being traded through powerful blows keeping rallies short until Hirsch emphatically ended the match's first lengthy exchange to level scores at 14 apiece.
Germany gained the lead at the second technical timeout through their impregnable frontline as the set continued to see-saw down the stretch. As they threatened to earlier in the stanza, Bulgaria took advantage of a suddenly wayward Germany to reel off four straight points to take a 22-18 lead and they shortly after closed out the first set through another German error.
After such a poor end to the first set, Hirsch fared better to start the second with a drilled spike down the line and he was aided by Marcus Bohme, who menaced at the net with his physicality. Unlike the first set, the play was marked by longer rallies as both defences were impressively resilient.
Bulgaria were struggling to hold serve but Yordanov mustered several precise spikes to ensure his team thwarted Germany's push. But Bohme's height at the net continued to provide easy points for Germany, who opened up a handy 16-12 buffer at the second technical timeout.
Bulgaria kept fighting through the efforts of Valentin Bratoev, who found his groove after a sluggish start, but the deficit proved too difficult to overcome as Germany made the right plays - aided by poor Bulgarian serving - to level proceedings.
With the match at a delicate state, the standard lifted with both teams desperately hustling as testament to forlorn dives from Bratoev and libero Vladislav Ivanov. Yordanov was showcasing a nice blend of power and finesse to continue his terrific performance as Bulgaria rediscovered their earlier form with Nikolay Penchev and Alexs Grozdanov proving hard to pass at the net.
But Bulgaria couldn't shake off a determined Germany as scores deadlocked on several occasions during the tense juncture. In a see-sawing period, the play peaked with the teams exchanging moments of brilliance with Karlitzek thundering a spike countered by deft touch from Rozalin Penchev.
With scores level at 23 apiece, Bulgaria's veterans stood up with Yordanov and Bratoev producing spikes to deliver their team the third set and a stranglehold of the match.
In a mirror image of the previous sets, little separated the teams in the fourth set as struggles on serve continued to ensure a tight scoreboard.
Consecutive firecrackers from Gotsev, who had been quiet in the previous two sets, gave Bulgaria some momentum but Hirsch was rediscovering his radar as another tight stanza was unfolding. With Karlitzek lifting his output, Germany had the edge and ensured a decider when Uchikov, Bulgaria's leading VNL scorer who came off the bench in the fourth set, served long.
Germany threw away points through careless serves but they were finishing stronger as their formidable frontline thwarted Bulgaria's attacks. Consecutive spikes from a confident Karlitzek gave Germany a decisive 12-8 edge and they hung on to record a memorable comeback victory.
Bulgaria play hosts Iran on Saturday, while Germany faces bottom-placed Korea.