Synchrotron-based experiments in combination with optical measurements were used to explore the potential of a photovoltaic material based on silicon carbonitride (SiCN) thin films, in particular for the use in space solar cells. The large bandgap, SiCN films were fabricated using electron cyclotron resonance plasma-enhanced chemical vapour deposition (ECR-PECVD) followed by low-temperature annealing processes. X-ray absorption near edge structure (XANES) with excitations at the carbon, nitrogen, and silicon K-edges verifies that the presence of nitrogen tends to disrupt Si–C networks. This results in the enhancement of light absorption and bandgap widening, which is desirable for front emitters in all-silicon tandem solar cells. The ternary structure of SiCN allows bandgap engineering and tuning of the light absorption and refractive index through careful design of the composition. XANES showed that the thermal annealing at a medium temperature (500 °C) using N2 ambient promoted the formation of Si–Si and C–N sp2 bonds before disappearing in higher annealing temperatures. In our opinion unlocking the potential of robust SiC mixed with nitrogen in SiCN matrix has appeal in radiation-resistant solar cells, where it can serve as the top emitter layer in all-silicon tandem solar cells and at the same time benefits the antireflection properties.