A wartime commander of Bosnian Croat forces "drank poison" during a hearing at the United Nations war crimes tribunal at which his 20-year prison sentence was upheld, his lawyer said.
The officials were convicted four years ago of participating in an "ethnic cleansing" campaign against Bosnian Muslims during Bosnia's war.
Court proceedings into former Yugoslavian war crimes was suspended after a defendant drank from a small bottle and claimed he had poisoned himself.
The hearing was halted, and a court guard told reporters that Praljak was "receiving medical attention", says The Daily Telegraph.
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The judge presiding over the appeal quickly shut down the hearing, which took place at The Hague in the Netherlands, as the area was treated as a crime scene.
The suicide of Slobodan Praljak at the UN-mandated International Criminal Tribunal for the former Yugoslavia (ICTY) is a multifaceted scandal.
Croatian state TV reported that President Kolinda Grabar Kitarovic made a decision to cut short an official visit to Iceland and the government was holding an emergency session.
Tribunal spokesman Nenad Golcevski, when asked by AP if he could confirm the death, said: "I have no information to share at this point". Judges did overturn some of his convictions, but refused to reduce his overall sentence.
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He and six other Bosnian Croat political and military leaders had appealed against their 2013 convictions for involvement in the crimes.
The Tribunal was set up in 1993, while fighting still raged in the former Yugoslavia, and has indicted 161 suspects for war crimes and convicted 90 individuals.
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