Several palladium catalysts with bulky phosphine ligands other than t-Bu3P were investigated for Suzuki-Miyaura catalyst-transfer condensation polymerization (CTCP). When the model reaction of 2,S-dibromothiophene with phenylboronic acid ester was carried out with a variety of Pd precatalysts in the presence of K3PO4 as a base, we found that the use of di-tert-butyl(4-dimethylaminophenyl)phosphine (AmPhos) Pd as a precatalyst resulted in exclusive formation of diphenyl-substituted thiophene. Polymerization of thiophene monomer and fluorene monomer with an initiator generated in situ from AmPhos Pd precatalyst and 4-iodobenzonitrile proceeded via the CTCP mechanism, affording polythiophene (P3HT) and polyfluorene with low dispersity and controlled polymer ends. Furthermore, (tolyl)PdAmPhos(Br) (7) was synthesized, and its polymerization properties were investigated. We found that polymerization of thiophene monomer with a mixture of 7 and CsF that had been stirred for 1 h prior to polymerization afforded P3HT with the dispersity of 1.18, which was considerably narrower than that in the case of CTCP with PhPd(t-Bu3P)Br. Block copolymerization of thiophene monomer and fluorene monomer with 7 proceeded irrespective of the polymerization order, in contrast to PhPd(t-Bu3P)Br-catalyzed block copolymerization, in which only chain extension with thiophene monomer from a polyfluorene propagating end took place and the reverse chain extension did not.