The South has previously imposed sweeping sanctions against companies based in the North, but this is the first time such measures have been taken against a group or individual outside the Korean peninsula.
Syria's Scientific Studies and Research Center and three Taiwanese companies -- Global Interface Company Inc, Trans Merits Co and Trans Multi Mechanics Co -- were blacklisted, Seoul's foreign ministry said in a statement.
Three Taiwanese individuals, including Tsai Hsein-Tai, Su Lu-Chi and Chang Wen-Fu, were also put on the blacklist, it said, without elaborating on them or the nature of their alleged involvement.
Violators face a prison term of up to three years or a maximum of 300 million won (US$270,000) in fines.
Under UN sanctions, South Korea has blacklisted 12 individuals and 20 organisations in the North over the years, following a series of nuclear and missile tests staged in violation of international resolutions.
South Korea maintains separate sanctions over the 2010 sinking of one of its warships, the Cheonan, which effectively froze all trade and investment with North Korea.
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