In this work, we have developed a hybrid one-step co-sputtering/evaporation Cu(In,Ga)Se2 (CIGS) process, where Cu, In and Ga are sputtered simultaneously with the thermal evaporation of selenium, thus avoiding the H2Se use. An appropriate control of the selenium flux is very important to prevent the target poisoning and hence some material flux variations. Indeed, the control of the CIGS composition must be rigorous to ensure reproducible solar cell properties. In this regard, a study of the correlations between plasma species and thin film composition, structure and morphology has been performed by varying power values and Se evaporation temperature in the 170 to 230 °C range. We started by studying the plasma with a powerful technique: optical emission spectroscopy, following light emissions from different plasma species: sputtered Cu, Ga, In but also evaporated Se. Hence, we determined the Se flow threshold avoiding target poisoning and the main parameter controlling the CIGS composition. Obviously, we also focused our interest on the material. We measured film composition and thickness of the samples with X-ray fluorescence and by energy dispersive X-ray. Different phases formed during the process were identified by Raman spectroscopy and X-ray diffraction. The optoelectronic cell properties showed promising efficiency of 10.3% for an absorber with composition ratios of [Cu]/([In] + [Ga]) = 1.02 and [Ga]/([In] + [Ga]) = 0.44. Finally, this work shows that we are able to control this hybrid process and thus the structure and composition of CIGS thin film for industrial transfer in the photovoltaic field.