Poroshenko made the announcement at a televised event in the Black Sea port alongside the reformist Saakashvili, calling the ex-Georgian president a "great friend of Ukraine".
"There remain a large number of problems in Odessa: preserving sovereignty, territorial integrity, independence and peace," Poroshenko said.
"But maybe the biggest challenge is another war-- a war against corruption, a war against injustice, a war against the unreformed economy."
The controversial announcement of the flamboyant Saakashvili as head of the southern coastal region is a pointed signal from Kiev to Moscow that it remains set on its pro-European course despite a bloody separatist conflict in the east blamed on the Kremlin.
"Together with the president and his team we are all going to build a new Ukraine," he said.
During his time at the helm in Georgia, Saakashvili, 47, became an arch-nemesis of the Russian leadership as he dragged his tiny ex-Soviet homeland out of Moscow's orbit and closer to the West after taking power in a popular revolution in 2003.
The collapse in relations spiralled into open conflict in 2008 when Russia defeated Georgia in a five-day war over the breakaway region of South Ossetia.
Saakashvili -- who left power in 2013 -- ruffled a lot of feathers with his radical reforms and clampdown on corruption in Georgia and is a deeply divisive figure there.
He has recently been living in exile after authorities last year issued an arrest warrant for him on abuse of power charges that he insists are politically motivated.
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