This work describes a new system using real time spectroscopic ellipsometer with simultaneous electrochemical and electrochemical quartz crystal microbalance (EQCM) measurements. This method is particularly adapted to characterize electrolyte/electrode interfaces during electrochemical and chemical processes in liquid medium. The ellipsometer, based on a rotating compensator Horiba Jobin-Yvon ellipsometer, has been adapted to acquire Psi-Delta spectra every 25 ms on a spectral range fixed from 400 to 800 nm. Measurements with short sampling times are only achievable with a fixed analyzer position (A=45 degrees ). Therefore the ellipsometer calibration is extremely important for high precision measurements and we propose a spectroscopic calibration (i.e., determination of the azimuth of elements according to the wavelength) on the whole spectral range. A homemade EQCM was developed to detect mass variations attached to the electrode. This additional instrument provides further information useful for ellipsometric data modeling of complex electrochemical systems. The EQCM measures frequency variations of piezoelectric quartz crystal oscillator working at 5 MHz. These frequency variations are linked to mass variations of electrode surface with a precision of 20 ng cm(-2) every 160 ms. Data acquisition has been developed in order to simultaneously record spectroscopic ellipsometry, EQCM, and electrochemical measurements by a single computer. Finally the electrodeposition of bismuth telluride film was monitored by this new in situ experimental setup and the density of electroplated layers was extracted from the optical thickness and EQCM mass.