Upon treatment of cyclic 1,2-bis(silylethynyl)benzenes with lithium naphthalenide, the intramolecular reductive cyclization proceeds in an endo–endo mode to produce 1,4-dilithio-2,3-disilylnaphthalenes, which are transformed into a series of 1,4-difunctionalized 2,3-disilylnaphthalenes.