By use of the organolanthanide catalysts Me2Si(C5Me4)(NAr)Lu(CH2SiMe3)(THF) and (C5Me5)2LaCH(SiMe3)2, carbazole-substituted phenyl enynes (Z)-CPEY and (E)-CPEY were synthesized, respectively, with excellent regio- and stereoselectivity through the catalytic dimerization of the corresponding terminal alkyne. These new pi-conjugated compounds, in particular, the (E)-enyne isomer (E)-CPEY, act as an excellent single-emitting component for white organic light-emitting devices (WOLEDs), as a result of combination of the blue emission from an isolated molecule with the longer-wavelength emissions (green and orange-red) from excimers. The (E)-CPEY-based double-layer device emitted almost pure white light with CIE coordinates of (0.32, 0.33), maximum brightness of 1395 cd m-2, and maximum current efficiency of 2.07 cd A-1. This is perhaps the purest white emission ever reported for a single-emitting-component WOLED. The quality of the white emission remained almost unchanged under varying driving voltages, demonstrating an advantageous potential of single-emitting-component WOLEDs.