Ahmed Gaddaf al-Dam was Tripoli's special envoy to Cairo for many years and left Libya for Egypt shortly after the 2011 uprising against Col Gaddafi.
Although sought by the Libyan authorities, the charges against him are unknown.
Egyptian security forces surrounded his Cairo home and there was an exchange of fire before he surrendered.
The circumstances surrounding the arrest remain unclear.
Vehicles of the Egyptian security forces had been sent overnight to Mr Gaddaf al-Dam's home in the Zamalek neighbourhood of the Egyptian capital.
Mr Gaddaf al-Dam told foreign media outlets that his guards had clashed with the Egyptian forces as they were unsure of their identity. It is unclear if anyone was injured.
Pictures then showed a smiling Mr Gaddaf al-Dam in a car, waving to the camera as he left the home.
Mr Gaddaf al-Dam played down the arrest, saying he was going voluntarily to Cairo's prosecutor general with his lawyers "to file a complaint".
Mr Gaddaf al-Dam was a high-profile figure under Col Gaddafi, says the BBC's Libya correspondent, Rana Jawad.
After arriving in Egypt in 2011, Mr Gaddaf al-Dam initially claimed he had defected, but took a more neutral stance weeks later, fuelling suspicion in Libya that he was still working for Col Gaddafi - an accusation he has denied in the past.
Libya has asked Egypt to hand over dozens of Libyans affiliated with the Gaddafi regime.
The arrest comes on the second anniversary of the start of the Nato air campaign in Libya that helped rebels in their fight against Col Gaddafi.
Former French President Nicolas Sarkozy, who championed the intervention, is in Tripoli for the day, meeting Libyan Prime Minister Ali Zeidan.
Mr Zeidan confirmed Mr Gaddaf al-Dam's arrest and thanked the Egyptian authorities for their "judicial cooperation".
Source: BBC News
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