A cornerstone of the smart grid is the advanced monitorability on its assets and operations. Increasingly pervasive installation of the phasor measurement units (PMUs) allows the so-called synchrophasor measurements to be taken roughly 100 times faster than the legacy supervisory control and data acquisition (SCADA) measurements, time-stamped using the global positioning system (GPS) signals to capture the grid dynamics. On the other hand, the availability of low-latency two-way communication networks will pave the way to high-precision real-time grid state estimation and detection, remedial actions upon network instability, and accurate risk analysis and post-event assessment for failure prevention. In this chapter, we firstly modelling spatio-temporal PMU data in large scale grids as random matrix sequences. Secondly, some basic principles of random matrix theory (RMT), such as asymptotic spectrum laws, transforms, convergence rate and free probability, are introduced briefly in order to the better understanding and application of RMT technologies. Lastly, the case studies based on synthetic data and real data are developed to evaluate the performance of the RMT-based schemes in different application scenarios (i.e., state evaluation and situation awareness).