Police fired tear gas at stone-throwing, masked protestors who had smashed windows and torched several cars and bins during a "No Expo" march which organisers said had brought 30,000 people onto the streets.
Water cannons were used to put out blazes, including one at a bank branch where the wall had been graffiti-ed with the words: "You've skinned us, today you pay."
The violent scenes helped make it a distinctly bitter-sweet start to a six-month food-themed event Italy hopes will bolster its international standing and give a boost to the struggling economy.
But there was grumbling from participants over organisational problems which meant many of the pavilions and exhibits were not fully operational.
Ticketless visitors arriving by underground train faced 90-minute waits in the Spring rain to get into the custom-built, 110-hectare site.
That was due to a combination of ticketing software problems and long queues for the airport-style security scanners.
They told AFP organisers had been unable to provide them with security passes in time due to "backlogging" in the processing of participants.
"I have been going to world exhibitions since Montreal in 1967 and I have never seen anything like this. We're quite angry," said the woman who did not want to be identified.
Unable to have any of their craft items delivered, her son was carrying as many as he could in two large sacks.
Declaring the fest open, Prime Minister Matteo Renzi bullishly insisted Milan and Italy had defied the critics who had said they would never be ready in time.
