Syrian air-defense command units will be connected directly to Russian command posts with automated systems that at present are deployed only in Russian units, he said.
Syrian military had already been trained to use the system, which was set to be sent over in 2013 but was held up "at the request of Israel", Shoigu said.
Shoigu said the supply of S-300s to Syria will "calm down some hotheads" whose actions "pose a threat to our troops".
Shoigu said the S-300 would be delivered to Syria within two weeks.
"Moscow's decision to provide Syrian forces with S-300 air defense system and Russian personnel to operate them is aimed at making Israel more careful in the vicinity of Russian assets, while also controlling Syrian allies", Dmitri Trenin, director of the Moscow Carnegie Center, wrote in Twitter.
'In regions near Syria over the Mediterranean Sea, there will be radio-electronic suppression of satellite navigation, on-board radar systems and communication systems of military aviation attacking objects on Syrian territory, ' he said.
Russia's military Sunday blamed "misleading" information from the Israeli airforce for the downing of one of its planes in Syria last week, and denounced the "adventurism" of Israeli pilots. They also said the Israelis may have deliberately used the Russian plane as a cover, expecting that the Syrians would not dare to fire at their F-16 fighter jets with the Russian plane nearby.
An Israeli official said the information showed that the Russian plane was shot down because Syrian batteries had "fired recklessly, irresponsibly and unprofessionally, long after our planes were no longer there". Liability falls on Israel, the ministry said, because warning of the strike came just one minute in advance.
The Kremlin, meanwhile, accused the Israeli pilots of "premeditated actions" over the downing of the Russian surveillance plane last week and warned that the incident would harm relations between the two countries, AFP reported.
The incident was also the worst case of friendly fire between Russian Federation and Syria since Moscow's military intervention in the country in support of President Bashar al-Assad's forces in September 2015.
"According to information of our military experts, the reason [behind the downing] were premeditated actions by Israeli pilots which certainly can not but harm our relations", Kremlin spokesman Dmitry Peskov told journalists on Monday. However, the Kremlin also said Russia's decision was not targeted against anyone and only serves to protect Russian troops in Syria. Russian Federation will also jam the electronic communications of aircraft attacking targets in Syria, he said.
In April, Moscow previously vowed to transfer S-300 missiles to Assad following coalition strikes in Syria from the United States, France, and Britain.