The deal, which include a number of pacts signed between the two countries, allow for the sale of uranium to China for peaceful use only.
Australia is the world's largest source of uranium, and the deal would lead to exports of 20,000 tonnes of yellowcake to China each year, double Australia's current exports of the radioactive material.
Australian Foreign Minister Alexander Downer said he signed two agreements with his Chinese counterpart following a meeting between Chinese Premier Wen Jiabao and Australian Prime Minister John Howard, covering nuclear transfer and nuclear cooperation.
"These agreements will allow for the supply of Australian uranium to China's nuclear power program, and cooperation in peaceful uses of nuclear technology," Mr Downer said in a statement.
"These agreements are consistent with Australia's long-term policy of applying safeguards and restrictions on uranium exports.
"The agreements also further build on and consolidate 25 years of development of safeguards requirements since agreements with other nuclear weapon states were first negotiated."
Mr Downer said there were clear environmental benefits in China diversifying from fossil fuels to low greenhouse-emission technologies such as nuclear power.
"Having the world's largest uranium resources, Australia has a particular responsibility and opportunity to consolidate its position as a secure supplier of energy resources, and leads by example in the application of strict safeguards," Mr Downer said.
He said the co-operation agreement provided for collaboration in peaceful applications of nuclear equipment and technology.
Officials said shipments would not start for at least another four years or so, as Australia's current production of uranium is already committed in existing contracts.
China has promised it would only use the Australian fuel for peaceful purposes and not towards any weapons program, saying it takes seriously its obligations as a member of the International Atomic Energy Agency and as a signatory to the nuclear non-proliferation treaty.
"This (uranium) is solely for peaceful purposes," Mr Wen told a media conference following the signing of the agreement.
"We must proceed with our co-operation in this field on the basis of mutual respect, mutual benefit and equality," he said through an interpreter.
Mr Howard said he was satisfied safeguards would be enforced.
"It's on that basis that the agreements have been signed," he told reporters.
Mr Wen is in Australia on a four-day visit aimed at boosting bilateral ties, including the rapidly growing trade relations between the two countries.