Electron spin resonance and electronic absorption spectra were measured to obtain structural information concerning the out-of-plane anisotropy of Cu(II) 1,4,8,11,15,18,22,25-octaalkoxyphthalocy (CnPcCu: n = 6, 10, 18) in Langmuir-Blodgett (LB) films. It was revealed that tilt angles with respect to a substrate surface and the aggregation mode of the macrocyclic rings in LB films depend on the length of alkoxy substituents as consistent with our previous results from pi-A isotherms, UV-visible absorption spectra and Brewster angle microscopy measurements.