Understanding molecular structures can play a critical role in revealing many important chemical and biological phenomena. X-ray crystallography and NMR methods, two of the most common structural tools, cannot reveal all unknown molecular structures due to the restriction of sample form or low time resolution, respectively. Motivated by the need of a new approach to reveal structures that are currently not feasible by these traditional techniques, this thesis has developed a uniquely designed ultrafast multiple-mode multiple-dimensional vibrational spectroscopy (MDVS) to conquer the limitations of traditional methods. The MDVS technique has also been applied to study molecular structures under various condensed phases, and facilitate the understanding of various chemical mechanisms in this thesis. Chapter 1 gave a brief review of the current common structure tools that have been used by chemists. Their advantages and disadvantages were compared to bring up the challenges that a new generation of structure tool needs to conquer. Chapter 2 gave a detailed description of the new design of our multiple dimensional vibrational spectroscopy and its theoretical basis on how it can be used to reveal molecular structures. Chapter 3 gave an example of how the MDVS reveals the molecular conformations for molecules in various condensed phases. Chapter 4 showed another application of MDVS in revealing an intermediate’s structure during a real catalytic reaction for hydrogen generation. Chapter 5 was inspired by the potential application of formic acid as a great hydrogen chemical storage material demonstrated in Chapter 4, we continued working on developing and optimizing hydrogenation catalysts with even better efficiency and long lifetime.