This article describes novel composite thin films consisting of GaN, C, and Ga (termed "GaCN", as an analogue to BCN and other carbonitrides) as a prospective material for future optical applications. This is due to their tunable refractive index that depends on the carbon content. The composites are prepared by introducing alternating pulses of trimethylgallium (TMG) and ammonia (NH3) on silicon substrates to mimic an atomic layer deposition process. Because the GaCN material is hardly reported to the best of our knowledge, a comprehensive characterization is performed to investigate into its chemical nature, primarily to determine whether or not it exists as a single-phase material. It is revealed that GaCN is a composite, consisting of phase-segregated, nanoscale clusters of wurtzitic GaN polycrystals, in addition to inclusions of carbon, nitrogen, and gallium, which are chemically bonded into several forms, but not belonging to the GaN crystals itself. By varying the deposition temperature between 400 and 600 °C and the NH3 partial pressure between 0.7 × 10-3 and 7.25 mbar, layers with a wide compositional range of Ga, C, and N are prepared. The role of carbon on the GaCN optical properties is significant: an increase of the refractive index from 2.19 at 1500 nm (for carbon-free polycrystalline GaN) to 2.46 (for GaCN) is achieved by merely 10 at. % of carbon addition. The presence of sp2-hybridized C=N clusters and carbon at the interface of the GaN polycrystals are proposed to determine their optical properties. Furthermore, the formation of the GaN polycrystals in the composite occurs through a TMG:NH3 surface-adduct assisted pathway, whereas the inclusions of carbon, nitrogen, and gallium are formed by the thermal decomposition of the chemisorbed TMG species.