OLED - which means organic light-emitting diode - is more energy efficient than LCD (liquid crystal display) and plasma-based alternatives. LG's model will be sold in South Korea first with other markets, including Europe, to follow thereafter. Both LG and Samsung announced 55in OLEDs last year, but LG is the first to make its available.
The firms showcased their televisions at last January's Consumer Electronics Show (CES) in Las Vegas, but until now neither company had managed to get a product to market. LG's headstart on its rival helped give it a 5.4% share price boost on Wednesday.
The 1080p (1920 x 1080 pixels) OLED television will sell for 11 million won ($10,300; £6,300). Analysts said the technology was unlikely to become more affordable until at least 2015 - but that this latest release was more about cementing LG's position as a market leader.
That said, global sales of OLED televisions are expected to grow to 1.7 million by 2014, according to research firm DisplaySearch. OLED screens have been touted as the successor to the popular liquid crystal displays (LCD). The technology allows for the display of darker and deeper blacks, and can be made thinner than competing display methods.
Source: BBC News