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"I am resigning as member of MCA and with the permission of PKR's de facto leader, I'm announcing that I'm joining PKR," he told a crowd of 1,000, which responded with shouts of 'reformasi'.
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He and PKR de facto leader Anwar Ibrahim appeared together at the PKR's 'The Truth Behind the Scandals: Perak, PKFZ and the BN Conspiracy' forum in Sunway Resort Hotel & Spa.
The forum participants applauded as Chua and Anwar entered the hall at 3.30pm.
A banner 'Congratulations to Chua for joining PKR' greeted the MCA leader as he walked in.
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He added that the death of Teoh Beng Hock, the political aide of Selangor executive councillor Ean Yong Hian Wah, was the “tipping point” in his decision to defect to the opposition.
Teoh's body was found on Thursday sprawled on the roof of an adjacent building after he had undergone questioning late into the night at the offices of the Malaysian Anti-Corruption Commission (MACC).
In joining PKR, Chua said he was taking a "new journey, a journey of change".
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In a short speech, both Yeoh and Yap also announced they were joining PKR which drew a thunderous applause from the crowd.
Malaysiakini has two days ago reported that Chua would be defecting to PKR.
Pakatan seeks to regain momentum
Chua had on Thursday called an emergency meeting of his Bakri MCA division where he resigned as its division chief after 23 years.
He urged members of the division to give their undivided support to MCA president Ong Tee Keat.
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Chua, 64, had contested for the MCA president's post twice and lost to two Ongs - Ong Ka Ting in 2005 and Ong Tee Keat in 2008.
Chua was not picked to defend his Bakri parliamentary seat in the last general elections.
The seat was subsequently won by DAP's Er Teck Hwa. Bakri is the sole parliamentary seat in Johor which fell to the opposition in the 2008 general elections.