Chemical deintercalation of lithium ions was attempted on Li₂MoO₃ with a structure related to the α-NaFeO₂ type structure. The lithium ions in Li_2-xMoO₃ were removed up to x=0.77 by oxidation, and its structure remained almost unchanged. The evolution of the lattice parameters for deintercalation compounds was divided into two parts; the regions of 0<x≤0.51 and 0.51<x≤0.77. In the first region, both a- and c-axes increased with an increase of x. In the second region the a-axis increased with increasing x, while the c-axis remained unchanged. This behavior could be explained by the existence of Mo-Mo bonding and immigration of lithium ions from the ((Li_1/3Mo_2/3)O₂)n layer to the interlayer spaces. Magnetic properties of Li_2-xMoO₃ exhibited temperature-independent paramagnetism.