1-Bora-4-tellurocydohexa-2,5-diene undergoes sequential [4 + 2] cydoadditions/alkyne-elimination reactions to incorporate 2 equiv of terminal alkyne with the loss of diarylalkyne, affording access to a series of 11 new tellurium-boron heterocycles. These alkyne exchange reactions proceed regioselectively and can tolerate a variety of functional groups, thus providing the potential for further derivatization. The mechanism of the exchange reaction is confirmed by a DFT study to involve the interaction of the Te and B with the alkyne in a frustrated Lewis pair fashion in the transition states.