Si-based total internal reflection (TIR) bio/chemical sensor presents an attractive alternative to Surface Plasmon Resonance (SPR) technology due to a relatively simple optical arrangement and technological implementation, as well as a relatively easy bio/chemical immobilization on Si/SiO(2) surface with a number of novel attractive applications. This sensor is based on the control of phase difference between p- and s-polarized components of light reflected from Si/air or Si/water interface in TIR geometry and a high sensitivity of the sensor is granted by a high refractive index of Si (3.56 at 1200 nm). We study properties of TIR sensors in a configuration of spectral phase detection and identify conditions of maximal phase sensitive response. We also experimentally show that the detection limit of Si-based TIR sensor can be lowered down to a level of detection of commercially available SPR devices (10(-6) Refractive Index Units, RIU) under the use of a proper low-noisy method of the phase control. The concept of Si-based TIR opens attractive prospects for the miniaturization of sensor devices, taking advantage of the advanced state of development of Si-based microfabrication technologies, while the proposed spectral phase detection scheme offers much easier packaging and calibration steps.