The new government, appointed earlier this week after Assad's June re-election, takes office as the death toll in the country's conflict since March 2011 soars past 191,000.
The crippling violence has decimated the country's economy and displaced approximately half its population, including three million Syrians who have taken refugee abroad.
Assad urged the new government to "provide a new vision," state news agency SANA reported, and to avoid the "negatives of the previous stage."
He said the government's success would depend on "earning the trust of citizens through transparency and credibility," SANA said.
"This issue is being addressed by the defence ministry and the army... At the same time, it is important to continue with national reconciliation," he said.
The new government includes 11 new ministers, with most of the changes involving finance and the economy.
Assad selected the new cabinet after being elected in the country's first multi-candidate presidential vote earlier this year.
The vote was dismissed as a "farce" by much of the international community and the opposition and was held only in government-controlled territory.
The government "must be decisive in the fight against corruption and hold the corrupt accountable," SANA quoted him as saying.
Syria's conflict has plunged half the population into poverty, according to researchers, with some 20 percent living in "abject poverty."
Unemployment stood at around 54 per cent at the end of 2013, though it was as high as 65 per cent in some places.
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