"I am expecting (it)", he said.
The attackers stormed two Syrian security offices in Homs, killing dozens with gunfire and explosions, including a senior officer, and prompting airstrikes against the last rebel-held enclave in the western city.
Syrian government and opposition delegates were not yet ready to enter into substantive talks about political transition and peace in Syria, as they tried to agree on a procedure for their Geneva negotiations. Do they mean Friends of Syria?
Asked if the attacks would affect the UN-sponsored talks, Staffan de Mistura said: "I hope not, but it was tragic".
Factions are drifting away from the exiled opposition leadership and instead moving closer to ultraconvservative groups such as the Ahrar al-Sham and the al-Qaeda linked Jabhat Fateh al-Sham.
Today, Mr de Mistura is to hold bilateral talks on procedure with the government and opposition delegations.
The groups that include Human Rights Watch, Amnesty International and Physicians for Human Rights say the priorities are "to end unlawful attacks and to ensure aid access and safe passage for fleeing civilians, detainee rights, justice, and security sector reform. They failed to control Iran", Hariri said, referring to another key Assad backer.
Meanwhile, the lead negotiator of the opposition group, Nasr al-Hariri, told reporters that the peace talks should prioritise finding a political transition in the country, which Assad's side would not agree to.
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"What happened today could be counted as liquidation by the regime of [detainees] who are wanted by worldwide courts". Bashar al-Ja'afari, Syria's United Nations ambassador who is one of the strongest defenders of Assad's government, is again leading Damascus' delegation.
Though the opposition has called for direct negotiations, the United Nations mediator said that there still was work to be done to get there, and said he was planning to resume bilateral meetings on Friday.
De Mistura was preparing more separate meetings with Syrian government and opposition negotiators.
Speaking to Al Jazeera in Geneva, Issam al-Reis, spokesperson for the Southern Front branch of the FSA, accused the Assad government of staging Saturday's attacks in Homs to influence the Geneva talks.
These are the first UN-mediated negotiations on Syria in nearly a year, during which time the military and geopolitical context has changed massively.
The Astana talks ushered in a shaky ceasefire which excludes hard-line jihadist groups such as Islamic State, and fighting continued in various parts of Syria on Thursday.
He took note of the presence of diplomats from the International Syria Support Group, which unites regional and world powers and is led by the United States and Russian Federation.