The present invention discloses a non-invasive method of measuring skin thickness and blood glucose concentration of a subject by a Raman system. The advantage of the present invention is that a single Raman spectrum is used to measure both the skin thickness and glucose concentration. The skin thickness and Raman intensity retrieved from the same Raman spectrum are both utilized to yield a more accurate blood glucose concentration. The present invention also discloses a Raman system for measuring physiological data of a subject. It comprises a Raman spectroscopic unit and a signal processing unit.