Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution Of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/ CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide v(3)-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm-1 were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the v(3)-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated Co-2 and H2O regions.