MPs on Tuesday will begin a two-day debate on the bill to trigger Article 50 with discussions on the so-called ‘Brexit bill’ likely to continue until midnight.
The bill is expected to easily pass the House, helped by Labour leader Jeremy Corbyn enforcing a three-line whip on MPs – which has already led to multiple frontbench resignations.
Speaking on Radio 4’s Today programme, Mr Smith said he would defy Mr Corbyn's orders and vote against the bill, as he accused the PM of "dissembling" on the issue.
"I fear that we are still being lied to, like during the referendum campaign, and lied to still about how easy this is going to be," he said.
Owen Smith has made clear his opposition to Brexit
I fear that we are still being lied to, like during the referendum campaign, and lied to still about how easy this is going to be
He also said, mischievously, that he hoped the PM would support his amendment to the Article 50 bill for a second referendum.
Mr Smith’s Pontypridd constituency voted Leave but he has made clear he will defy their will and vote against triggering Article 50.
Mr Smith was among the 22 Labour MPs to lend their support to a wrecking amendment to the Bill, although it is highly unlikely to pass.
It calls on MPs to throw out the Bill at second reading "because the Government has failed to give assurances which safeguard British interests in the single market, and because the Government has failed to provide assurance that either Parliament or the UK electorate will have the ability to determine whether the UK should seek to withdraw from the single market in accordance with Article 127 of the EEA Agreement".
The 46-year-old MP has embraced his title as the ‘Remoaner-in-chief’ and is adamant in his belief Brexit will damage the EU.
Jeremy Corbyn has instructed his MPs to vote for Article 50 – causing a series of resignations
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“I have reached the decision that whatever the impact on my career, however difficult it may be to swim against the Brexit tide, I cannot, in all conscience, stand by and wave through a course of action that I believe will make our people poorer and our politics meaner,” he told The Guardian.
Radio 4 listeners hit out at the Labour politician. One accused Mr Smith of “breathtaking hypocrisy”.
Another said: “Owen Smith with a wonderfully sneering interview this morning. Calls leave voters of all parties narrow-minded. 'I know best'."
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Gareth Watkins said: “Labour MPs should vote with their constituents. @OwenSmith–MP proving again why he should be leader.”
“The voters have told him we know him [sic] wrong, and he elbows in to spoil and meddle #Brexit broth at every chance,” another tweeted.
Heather Neagle tweeted: @OwenSmith_MP doing that patronising, paternalistic thing that Labour MPs do all the time. Just respect the vote #radio 4.”