Formation of the Langmuir monolayer, and structure of the Langmuir-Blodgett (LB) films of Tetra-t-butyl metallophthalocyanines (MTBP) were investigated by the surface pressure-area isotherm and X-ray diffraction (XRD) method, respectively. We obtained a well-defined monolayer on the subphase at concentrations of 5 .EM for the CuTBP and 2.5μM for Co, Zn, and VOTBP solutions. CuTBP yields a well-defined monolayer, due to formation of twodimensional aggregates on the surface where the limiting area of the monolayer is much greater than the intrinsic side area of MTBP. Since intensity of the XRD was so small, the LB layers with one to three layers may not be welloriented. An annealing procedure refined molecular organization of LB films significantly.