Alkyne cross-metathesis of molybdenum car-byne complex [TolC Mo(OCCH3(CF3)(2))(3)]center dot DME with 2 equiv of functional ynamines or ynamides yields the primary cross-metathesis product with high regioselectivity (>98%) along with a molybdenum metallacyclobutadiene complex. NMR and X-ray crystal structure analysis reveals that ynamides derived from 1-(phenylethynyl)pyrrolidin-2-one selectively cleave the propagating molybdenum species in the ring opening alkyne metathesis polymerization (ROAMP) of ring-strained 3,8-dihexyloxy-5,6-dihydro-11,12-didehydrodibenzo- [a,e][8]annulene and irreversibly deactivate the diamagnetic molybdenum metallacyclobutadiene complex through a multi-dentate chelate binding mode. The chain termination of living ROAMP with substituted ethynylpyrrolidin-2-ones selectively transfers a functional end-group to the polymer chain, giving access to telechelic polymers. This regioselective carbyne transfer strategy gives access to amphiphilic block copolymers through synthetic cascades of ROAMP followed by ring-opening polymerization of strained epsilon-caprolactone.