Forward Adem Ljajic and defender Branislav Ivanovic were also on target as the Serbians netted four of their goals in a lop-sided first half against the hapless Bolivians, who failed to qualify for the June 14-July 15 tournament in Russia.
Stung by a lacklustre 1-0 defeat against Chile on Sunday, Serbia coach Mladen Krstajic switched to a 4-2-3-1 formation with Ljajic playing behind Mitrovic and central midfielder Sergej Milinkovic-Savic deployed in a deeper role.
The rejigged line-up fired on all cylinders in the opening half as Mitrovic headed Serbia into an early lead and made it 3-0 with a clinical finish after Ljajic drilled in the second with a fine shot from 13 metres.
Ivanovic, who equalled former midfielder Dejan Stankovic's record of 103 international appearances, volleyed in the fourth shortly before halftime after Mitrovic found him unmarked with an overhead kick across the face of the six-yard box.
The Serbians took their feet of the gas early in the second half and Bolivia quickly took advantage as Jhasmani Campos poked the ball past goalkeeper Vladimir Stojkovic after a fine solo run in the 48th minute.
Bolivia keeper Guillermo Viscarra parried two stinging shots from Dusan Tadic but was powerless when Newcastle United striker Mitrovic curled a delightful shot from 20 metres past him to cap an outstanding individual performance.
Winger Filip Kostic missed two good chances to add to Serbia's tally as they upped the tempo in the closing stages, roared on by several hundred passionate fans in Graz.
Serbia's fine display is likely to leave Krstajic with selection dilemmas ahead of their opening Group E game against Costa Rica on June 17, as Milinkovic-Savic may now be preferred to Luka Milivojevic in central midfield.
Centre back Nikola Milenkovic, who won only his third cap, also looks set to get the nod ahead of more experienced players after a pair of rock-solid performances.
The Serbians also play Switzerland on June 22 and Brazil five days later.
(Writing by Zoran Milosavljevic in Belgrade; Editing by Christian Radnedge)
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