"The Liberal Democrats are delighted to announce that Bracknell MP Phillip Lee has joined the party," the Lib Dems said in a statement.
Johnson braced for a showdown in parliament on Tuesday over his Brexit plan in a vote that could derail Britain's exit from the European Union next month.
Pound slides to three-year low as no-deal Brexit battle begins
Members of Johnson's own Tory party, including Lee, have worked with opposition lawmakers to draft a bill to force him to delay Brexit if he cannot agree divorce terms with the EU in time.
Johnson has warned he will prevent any Tory parliamentarians who support the bill from standing for the party in any upcoming election, which is looking increasingly likely.
UK PM Johnson threatens election ahead of Brexit battle in parliament
"This Conservative government is aggressively pursuing a damaging Brexit in unprincipled ways," said Lee.
"It is using political manipulation, bullying and lies. And it is doing these things in a deliberate and considered way," he added.
Liberal Democrat leader Jo Swinson said she was "delighted" by the defection.
"He shares our commitment to prevent a disastrous No Deal Brexit, and to stop Brexit altogether," she said.
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