In this work, a biosensing method based on in situ, fast, and sensitive measurements of ellipsometric parameters (Ψ, ∆) is proposed. Bare silicon wafer substrate is functionalized and used to bind biomolecules in the solution. Coupled with a 45° dual-drive symmetric photoelastic modulator-based ellipsometry, the parameters Ψ and ∆ of biolayer arising due to biomolecular interactions are determined directly, and the refractive index (RI) of the solution and the effective thickness and surface mass density of the biolayer for various interaction time can be further monitored simultaneously. To illustrate the performance of the biosensing method, immunosensing for immunoglobulin G (IgG) was taken as a case study. The experiment results show that the biosensor response of the limit of detection for IgG is 15 ng/mL, and the data collection time is in milliseconds. Moreover, the method demonstrates a good specificity. Such technique is a promising candidate in developing a novel sensor which can realize fast and sensitive, label-free, easy operation, and cost-effective biosensing.