skew-Tetramantane—diamond’s chiral core—previously only accessible from fossil fuels after elaborate separations, was selectively synthesized by a combination of visible-light photocatalytic reactions to modulate radical chemistry and catalyst-controlled C–H insertions. Operating under kinetic control, this stereoselective adamantalogous cage-extension strategy provides access to synthetic diamondoids beyond adamantane, diamantane and triamantane.