Ultraviolet-visible (UV-vis), infrared transmission, reflection-absorption (RA), and fluorescence spectra have been measured for one-, three-, and nine-monolayer Langmuir-Blodgett (LB) films of an azobenzenecontaining long-chain fatty acid (4-dodecyloxy-4′-(3-carboxytrimethyleneoxy)azobenzene, abbreviated 12A3H) at various temperatures to investigate dependences of phase transitions and annealing effects on the number of monolayers. The UV-vis spectra of the LB films have revealed that the fatty acid investigated forms H-aggregates in the LB films irrespective of the number of monolayers at room temperature. With a temperature increase the H-aggregate in the one-monolayer LB film gradually breaks into the monomers, while that in the three-and nine-monolayer LB films abruptly changes into the J-aggregate near 90°C. These observations show that the one-monolayer LB film does not have a clear order-disorder transition, while the three-and nine-monolayer films have a phase transition near 90°C. The infrared study has also given unambiguous evidence that supports this conclusion. For example, the peak intensities of CH 2 antisymmetric and symmetric stretching bands at 2920 and 2850 cm -1 in the transmission spectrum of the one-monolayer film gradually decrease with temperature, suggesting that the alkyl chain becomes tilted little by little with respect to the surface normal. In contrast to the one-monolayer film, the peak intensities of most of the infrared bands of the three-and nine-monolayer films undergo a marked change near 90°C. Therefore, it seems that the tilt angles of both the alkyl chain and chromophobic part change largely concomitantly with the conversion from the H-aggregate to the J-aggregate. Cyclic thermal treatment experiments for the UVvis spectra of the LB films show that the conversion from the H-aggregate to monomers in the one-monolayer film is nearly reversible, while annealing of the three-and nine-monolayer films causes a transition from the J-aggregate to another J-aggregate. The latter J-aggregate is further converted to the original H-aggregate by leaving the LB films in the atmosphere or irradiating them with UV laser light.