To investigate the effect of alkyl chain length and adsorption time on the charge-transfer complex formation, ultraviolet-visible absorption and inelastic electron tunneling (IET) spectroscopy measurements were carried out for the tetramethylphenylenediamine (TMPD; donor molecule) adsorbed dodecyl-, pentadecyl- and octadecyl-tetracyanoquinodimethane (TCNQ) Langmuir-Blodgett (LB) films. In the optical absorption spectra, the main peak of LB films shows a red-shift depending on alkyl chain length and adsorption time. Furthermore, the dependence on alkyl chain length and adsorption time are also shown in the IET spectra. These results demonstrate that adsorption LB methods enable to control the adsorption ratio of functional molecules and the CT complex formation.