Although Katsav's role is largely ceremonial, his comments on Thursday were in stark contrast to the reaction of Foreign Minister Silvan Shalom, who said he would not contemplate the resumption of negotiations.
In an interview with the Maariv newspaper, Katsav expressed scepticism about Syria's intentions but said Israel should not automatically snub peace overtures.
"In my opinion it is important to carefully examine Asad's intentions, whether he really wants peace or only wishes to improve his international image," he said.
Terje Roed-Larsen, the UN envoy for the Middle East, said on Wednesday that Syrian President Bashar al-Asad was ready to reopen negotiations with Israel "without conditions".
"President Asad had reiterated to me today that he has an outstretched hand to his Israeli counterpart, that he is willing to go to the table without conditions," Roed-Larsen said after talks with the Syrian leader.
Shalom, however, poured cold water on the idea of resuming talks after a near five-year impasse by repeating accusations that Syria was harbouring leaders of Palestinian resistance groups such as Hamas.
Observers believe Sharon will not
engage Syria in peace talks now
"We can't talk about peace and allow terrorism to be conducted on their territory," Shalom told public radio.
Peace talks over the fate of the strategic Golan Heights between Syria and Israel broke down in January 2000 shortly before Ariel Sharon became Israeli prime minister.
The Golan Heights were seized by the Jewish state in the 1967 war and later annexed.
Observers believe that Sharon will not allow himself to get bogged down in peace negotiations with Syria or consider a withdrawal from parts of the Golan Heights while trying to carry out his planned pullout from the occupied Gaza Strip.
Meanwhile, Katsav refused to rule out the possibility of giving jailed West Bank Fatah leader Marwan al-Barghuti a presidential pardon.
Marwan Barghouti is considered
a charismatic Palestinian leader
"Barghuti is a murderer who has been sentenced to life terms in prison. If he applies for a pardon, I will discuss it," Katsav told the Israeli daily newspaper Maariv on Thursday.
Al-Barghuti, who is widely seen as the inspiration behind the
Palestinian uprising, was sentenced by an Israeli court in June to five life terms for alleged murder.
The Palestinian leader says his people have a legitimate right to resistance.
Nevertheless, he is by far the most popular Palestinian politician in the aftermath of veteran leader Yasir Arafat's death and many people have been pushing for him to run for the post of Palestinian Authority president from behind bars.