Interactions of Ni(0) and thiophene benzothiadiazole-thiophene (TBT) units during the Kumada catalyst transfer polycondensation (KCTP) of 2-chloromagnesio-5-bromo-3-hexylthiophene (1) are investigated. Monofunctional TBT initiator precursors are used for the external initiation of KCTP, and the mechanism of initiator activation and polymerization is elucidated using NMR and MALDI-ToF MS. We find that the activation of the TBT-bromide initiator precursor using nickel-diethylbipyridine (NiEt(2)bipy) occurs via a two-step pathway, in which NiEt(2)bipy coordinates to benzothiadiazole (B) first, followed by the elimination of butane and oxidative addition of liberated Ni(0)bipy into the terminal TBT-Br bond. It is shown that the B unit traps Ni(0) during the KCTP of 1, which results in significant termination, as derived from the degree of bromine-terminated chains. The ability of B units to trap Ni(0) is further illustrated by using a symmetric bifunctional Br-TBT-Br initiator precursor for the KCTP of 1, during which Ni(0) is not able to "ring walk" over the B unit to initiate polymerization at the other end of the chain. These results are important for the design of well-defined and electronically end-functionalized conjugated polymers, but also for understanding termination mechanisms in KCTP in general.