The polymerization of 2‐butene and its copolymerization with ethylene have been investigated using four kinds of dichlorobis(β‐diketonato)titanium complexes, ArN(CH2)3NArTiCl2 (Ar = 2,6‐iPr2C6H3) and typical metallocene catalysts. The obtained copolymers display lower melting points than those produced of homopolyethylene under the same polymerization conditions. 13C NMR analysis indicates that 9.3 mol‐% of 2‐butene units were incorporated into the polymer chains with Ti(BFA)2Cl2‐MAO as the catalyst system. With the trans‐2‐butene a higher copolymerization rate was observed than with cis‐2‐butene. A highly regioselective catalyst system for propene polymerization, ArN(CH2)3NArTiCl2 complex using a mixture of triisobutylaluminium and Ph3CB(C6F5)4 as cocatalyst, was found to copolymerize a mixture of 1‐butene and trans‐2‐butene with ethylene up to 3.1 mol‐%. Monomer isomerization‐polymerization proceeds with typical metallocene catalysts to produce copolymers consisting of ethylene and 1‐butene.