Hichilema, who has refused to recognise Lungu as president, was accused of deliberately endangering his life in the high-speed incident at the weekend.
"We have charged Hichilema and five others with treason," Zambian police chief Kakoma Kanganja told reporters in Lusaka.
"The opposition leader disobeyed police orders to give way to the presidential motorcade in an attempt to put the life of the republican president in danger."
The accused, who include Hichilema's aides, have also been charged with disobeying lawful orders and use of insulting language.
The state-owned Zambia Daily Mail said that Hichilema's motorcade ignored police attempts to clear the road between Limulunga and Mongu, 500 kilometres (300 miles) west of the capital Lusaka.
"The behaviour of Mr Hichilema and his cohorts was not only a senseless act of disrespect to the presidency but also endangered the life of the head of state and many other people," it said in an editorial.
More than 100 armed police surrounded Hichilema's house outside Lusaka early on Tuesday and tear gas was fired before a raid when he was taken into custody.
Hichilema has launched several legal attempts to challenge the August election result, which he lost narrowly.
He says that the vote was rigged and accuses Lungu of an unprecedented bout of political repression in Zambia, which has been known for its relative stability.
The election campaign was marked by clashes between supporters of Lungu's Patriotic Front (PF) party and the UPND.
Hichilema, a wealthy self-made businessman known as "HH", has run for president five times.
Last October, Hichilema and party vice-president Geoffrey Mwamba were arrested for unlawful assembly and sedition when they tried to visit supporters in jail.
Zambia, Africa's second biggest copper producer, recorded GDP growth of three per cent last year - its slowest rate since 1998.
"HH could be detained for some time, so this will suit the ruling party who want to silence the dialogue about the election result not being recognised," independent political analyst Neo Simutanyi told AFP.
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