The much-anticipated handset is expected to prompt a rush to Glasgow stores when it launches in the UK next month.
A host of new features were revealed at the global launch in New York, including a dual camera function that can take two pictures at once and "smart pause", which lets users pause a video by looking away from the screen.
JK Shin, president and head of IT and mobile communications at Samsung, said: "We have taken technology and innovation forward to help us get closer to what matters in life, to help us live a richer, simpler and more full life."
It will be on sale in the UK from April 26, and available through 327 mobile operators in 155 countries.
Samsung is said to be expecting sales of its new handsets to be up to 10 million per month.
Technology critics were lavish in their praise, with some predicting the S4 could take a large bite out of Apple's market share.
Telecoms expert at uSwitch Ernest Doku, said: "With brains as well as beauty, Samsung's effort looks set to be the biggest handset of the year – in spite of an inevitable iPhone sequel."