An “ink” solution based process, using spin-coating technique, followed by annealing in selenium environment with different temperature programs was utilized to prepare CIGSe thin films. Herein, the CuIn0.7Ga0.3Se2 nanocrystals were synthesized using ethanol - a “green” solvent. Three different solvents: 2-propanol, 2-methoxyethanol, and their 2 : 1 mixture (v/v ratio), were investigated as a dispersion medium for the as-synthesized CIGSe nanocrystals to form a stable ink solution. The last one- a mixture of 2-propanol : 2-methoxyethanol=2 : 1 (v/v), was found to be the most suitable. Furthermore, the influences of various annealing modes on the CIGSe grain size and density in the resulting film were also studied. The as-prepared CIGSe thin film was around 1μm thick and possessed a tetragonal structure. A newly developed cheaper and “greener” non-vacuum process was applied successfully from the synthesis of nanocrystals to the formation of ink solution, and produced high quality thin films; this opens a new route to the cost-competitive commercialization of CIGSe thin film solar cells.