In this work we have established that a new Schiff base (Z)-2-((pyridin-2-yl) methyleneamino) benzenethiol (2PMAB) prepared by reaction of 2-aminobenzenethiol with picolinaldehyde is a good electrode modifying agent to sense cholesterol. Glassy Carbon electrode surface has been modified with styrene film impregnated with 2PMAB. Ag+ ion has been attached to the S atoms of 2PMAB on the electrode surface resulting in modified electrode of the type GC/styrene/2PMABAg. Cholesterol imparts a significant change of 0.048V in redox potential of the modified electrode. For the GC/styrene/2PMABAg electrode the response time is 3 s, detection limit (3σ) 1.99X10-5 M; sensitivity 0.0722 V/mM and linear range is 3.96X10-5M to 37.03X10-5M. Moreover, fluorescence study of the compound is also done in presence of the soft metal Ag and analyte cholesterol which indicates a significant “turn off” (420nm) of the fluorescence intensity of 2PMAB in presence of Ag and “turn on” at a new wavelength (520nm) in presence of cholesterol when excited at 350nm.