The reaction between La atoms and 1,3-butadiene is carried out in a laser-vaporization molecular beam source. Metal-hydrocarbon species with formulas La(CH) (n = 2, 4, and 6) and La(CH) (m = 4 and 6) are observed with time-of-flight mass spectrometry and characterized with mass-analyzed threshold ionization spectroscopy. A lanthanum-benzene complex [La(CH)] is formed by 1,3-butadiene addition to lanthanacyclopropene [La(CH)] followed by molecular hydrogen elimination. Lanthanacyclopropene is an intermediate generated by the primary reaction between La and 1,3-butadiene. Two other intermediates produced by the La + 1,3-butadiene reaction are La[η-(1-buten-3-yne)] [La(CH)] and 1-lanthanacyclopent-3-ene [La(CH)]. The La(benzene) complex exhibits distinctive metal-ligand bonding from that of the three intermediates as shown by the adiabatic ionization energies and ground electron configurations.