CuInGaSe2 (CIGS) is a prominent thin-film photovoltaic material. However, commonly used physical vapour deposition and sputtering techniques used to fabricate CIGS thin-film photovoltaic (PV) devices are complex and expensive. Therefore non-vacuum deposition techniques such as paste coating, spray pyrolysis and electro deposition are gaining more attention in recent years. Our intention is to choose a low cost non-vacuum technique like mechano-chemical synthesis of CIGS powder, followed by screen printing. Mechano chemical synthesis is a process that induces physical and/or chemical change in the compounds by mechanical energy, such as pulverization, friction or compression. This method has some advantages for the mass production of CIGS solar cells, high productivity and short processing cycle time. In the present work CIGS powders suitable for screen-printing ink has been prepared by ball milling. High purity elemental copper granules (>99.9% pure), selenium and indium powders (>99.9% pure) and fine chips of gallium (>99.9% pure) were used as the starting materials. Ball milling was carried out for an optimized composition of CuIn0.75Ga0.25Se2 using a SPEX-8000 mixer/mill at 1200 rpm for 1.5 hours. X-ray diffraction analysis of the milled powder shows the presence of (112), (220)/ (204), (312)/ (116), (400) and (332) peaks corresponding to CIGS chalcopyrite structure with a preferential orientation along (112) peak. The average grain size calculated by Scherrer’s formula is about 12.24 nm. Crystallographic structure of the prepared CIGS powder was analyzed by Rietveld analysis using X-ray powder diffraction data. Geometry optimization of the structure was performed and the basic structural properties have been evaluated by density functional approximation and compared with experimental results. Density of states has been simulated for the same structure inorder to have a better understanding of the distribution of atomic orbitals. FESEM analysis shows the agglomeration of nano particles. Particle size varied from 11 to 30nm. Final composition of the milled powder studied by Energy dispersive X-ray analysis gives 24.39 at% Cu, 21.42 at% In, 7.22 at% Ga and 46.97 at% Se. HRTEM analysis reveals the presence of nano crystalline particles. The interplanar distance (d-spacing) corresponding to (112), (220)/ (204), (512)/ (417) and (620)/ (604) diffraction peaks has been estimated and compared with standard values and the corresponding diffraction pattern has been simulated with simulaTEM software. CIGS ink is prepared by proper mixing of the powder with a suitable organic binder (ethyl cellulose). Screen printing is carried out on glass substrates, followed by annealing at 5 different temperatures of 300,350,400,450 and 500 degrees, in order to form a porous CIGS film. XRD analysis was carried out to study the structure of screen printed CIGS.