The study on the shape evolution of metal nanoparticles (MNPs) is crucial to gain an understanding on controlling the shape and size of metal nanostructures. In this work, a detailed study on shape evolution of silver (Ag) nanospheres to nanoplates induced by hydrogen peroxide (H2O2) was performed. According to the growth mechanism of Ag nanoplates, the spectrophotometric method combined with chemometric analysis has potential to reveal the structural evolution process as observed by surface plasmon resonance phenomena. The extinction spectra of the evolving nanostructures were analyzed by factor analysis and error indicator functions. Five major components attributed to the different particle shapes and sizes were theoretically predicted. Furthermore, the concentration profiles and pure spectra of these components were resolved using multivariate curve resolution-alternative least squares (MCR-ALS) analysis. The evolution profiles show that the spherical Ag particles systematically evolved into plate structures of different sizes. Larger nanoplates were obtained when higher concentrations of H2O2 were employed. An evidence of nanoplate disintegration was observed when a large amount of H2O2 was employed. The predicted structural morphologies of each component given by chemometric calculation were in excellent agreement with those observed by transmission electron microscope (TEM) images.