In this work, we report how manganese phthalocyanine (MnPc) films obtained using the ultrasonic spray–pyrolysis technique at 40 °C deposited on glass substrate subjected to thermal annealing at 100 °C and 120 °C. The MnPc films were characterized using UV/Vis spectroscopy, Raman spectroscopy, X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). The absorption spectra of the MnPc films were studied in a wavelength range from 200 to 850 nm, where the characteristic bands of a metallic phthalocyanine known as B and Q bands were observed in this range of the spectrum. The optical energy band (Eg) was calculated using the Tauc equation. It was found that, for these MnPc films, the Eg has the values of 4.41, 4.46, and 3.58 eV corresponded to when they were deposited, annealing at 100 °C and 120 °C, respectively. The Raman spectra of the films showed the characteristic vibrational modes of the MnPc films. In the X-Ray diffractograms of these films, the characteristic diffraction peaks of a metallic phthalocyanine are observed, presenting a monoclinic phase. The SEM images of these films were studied in a cross-section obtaining thicknesses of 2 μm for the deposited film and 1.2 μm and 0.3 μm for the annealed films at 100 °C and 120 °C. Additionally, in the SEM images of these films, average particle sizes ranging from 4 to 0.041 µm were obtained. The results agree with those reported in the literature for MnPc films deposited by performing other techniques.