Atomization characteristics of liquid fuel sprays control combustion efficiency and emissions in engines. The present work is motivated by the need to study the atomization and spray structure of vegetable oil biofuels for which no data in the literature exists. In this work, various laser-based diagnostic techniques such as laser shadowgraphy, Particle/Droplet Image Analysis (PDIA) and Laser Sheet Dropsizing (LSD) are applied for studying atomization characteristics, tip penetration, droplet size and liquid volume fraction of Pongamia vegetable oil (SVO) and its blends with diesel. A constant volume high pressure spray visualization chamber is designed and fabricated to study SVO sprays at high gas pressure and temperature conditions. This optical chamber can be used for gas pressures up to 60 bar and temperatures up to 600 K. Optical access inside the chamber is provided through four quartz windows to perform various optical spray diagnostic studies. A high pressure spray injection facility based on components of common rail diesel injection system is designed. This facility can provide an injection pressure of up to 1700 bar with independent control over injection duration and timing. A marked difference is observed between diesel and SVO spray structures under atmospheric gas pressure condition. A very interesting observation related to the behavior of 100% SVO fuel when sprayed into atmospheric pressure is the presence of an intact liquid core even at injection pressure as high as 1600 bar. The presence of liquid core at high injection pressures is attributed to the high viscosity of SVOs and the non-Newtonian behavior of these oils under high pressure and shear. The spray characterization of the oil and its blends at high gas pressure shows that although the atomization is dramatically different from that at atmospheric gas pressure, it is still incomplete even at very high injection pressures. For a gas pressure of 30 bar, it is observed that the Sauter Mean Diameter (SMD) for Pongamia oil is more than twice that of diesel. A new method of simultaneously obtaining two-dimensional droplet size and quantitative liquid volume fraction data in sprays has been developed. Measurements with this method reveal a higher liquid volume fraction at the central axis of spray for Pongamia oil compared to that of diesel indicating potentially poor air-fuel mixing. The experimental data obtained and the spray tip penetration correlations developed for the vegetable oils and blends serve as useful inputs for fuel injection and engine system designers.