The national death toll since the elections is now about 800 |
Mugabe Were, a member of the Orange Democratic Movement (ODM) of the defeated candidate, Raila Odinga, was attacked outside his home, police said.
An ODM spokesman called for calm and restraint following the MP's death.
Meanwhile the parties will begin formal talks on Tuesday to resolve the crisis, mediated by former UN chief Kofi Annan.
A UN spokesman said the dialogue process would start at 1600 local time (1300 GMT) at a neutral location.
'Shun violence'
Mr Were is the first leading politician to have died amid violence that has gripped Kenya since December's poll.
Two gunmen shot Mr Were as he drove up to the gate of his house in the capital just after midnight, Kenya police spokesman Eric Kiraithe was quoted by the Associated Press news agency as saying.
ODM spokesman
"We are treating it as a murder but we are not ruling out anything, including political motives. We are urging everyone to remain calm," he said.
Mr Were, who represented Nairobi's Embakasai district, won a seat in the 27 December legislative election, which was held at the same time as the presidential vote.
ODM spokesman Tony Gachoka said: "The current situation makes one suspicious. All fingers will point at the government, and the government will have to show it is not involved."
Another ODM spokesman, Salim Lome, called on people "to be peaceful and to only respond to this kind of violence by shunning violence".
The appeal came amid reports of opposition supporters pouring onto the streets in several cities.
In the Kibera slum in Nairobi, eyewitnesses spoke of clashes between rival ethnic groups.
Members of President Mwai Kibaki's Kikuyu tribe have been fighting with Luos and Kalenjins who backed his rival, Mr Odinga, in last month's election.
International concern
Police fired tear gas and live bullets to disperse a crowd of about 100 opposition supporters who had gathered in the western city of Kisumu in a show of anger at Mr Were's killing, AFP news agency reported.
"First they started killing the ordinary people like us, now they are killing our leaders, we won't accept it," demonstrator Justus Othieno told AFP news agency.
The protest followed bloodshed in Kisumu and also in Eldoret.
Riots have also been ongoing in the towns of Naivasha and Nakuru in the Rift Valley, where dozens of people have been killed in five days of ethnic violence.
Plumes of smoke were seen rising from the lakeside at Naivasha, as crowds apparently looted the homes of people fleeing the violence.
Mr Odinga accuses Mr Kibaki of stealing the vote and has refused to recognise the result.
Analysts warn a cycle of violence is emerging amid the political impasse, where the pattern of attacks is followed by reprisals.
The former UN secretary general Kofi Annan has been trying to mediate a solution between the two sides.
He set Tuesday as a target for Kenya's government and opposition to name negotiators, in the hope that engaging in formal talks might make it possible to quell the violence.
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