New antimony(III) phthalocyanine complex under iodine vapor atmosphere, (SbIIIPc)(I3).½(I2), (1), was obtained. The (SbIIIPc)(I3).½(I2) crystallizes in the centrosymmetric space group of the triclinic system. The (SbPc)+ unit is non-planar Two inversion related (SbIIIPc)(I3) units interact each other via neutral I2 molecule yielding {[C32H16N8Sb](I3)}2(I2) dimeric aggregate. Resonance Raman spectroscopy was used to identification of the iodine forms in crystal. The aggregates related by translation in the direction of the a-axis form a stacking structure. However, within the stacks, the Pc rings are clearly shifted, so the π-π interactions is relatively very low, due to their non-planarity, as well as by only partial overlapping of the outermost six-membered rings of the adjacent back-to-back-oriented (SbPc)+ macrocycles. The interaction between the building units (SbPc)+, I3− and I2 were analyzed using the Hirshfeld surface and the analysis of the 2D fingerprint plots. Relatively low interactions of π…π result in its considerable solubility, which manifests itself particularly in the improvement of optical properties of solutions. UV–Vis absorption spectra of 1 were taken in DMSO and toluene solutions in the concentration range from 10−5 to 10−6 mol/l. No significant changes related to aggregation in solutions were observed. Diffuse reflectance spectroscopy (DSR) due to interactions between the molecules in solid-state, showed much wider bands compared to the UV–Vis bands of the complex in solution. Oxidation of (SbIIIPc)(I3).½(I2) in methanol solution by H2O2 yields SbVPc derivative. Both SbIII and SbV phthalocyanine derivatives absorb near infrared light (600–900 nm) which should be intriguing with the point of view of potential use as an infrared cut filter for plasma display and silicon photodiodes, and in addition to as photosensitizers for semiconductor lasers.