Three different luminescent silver nanoparticles(AgNPs) were synthesized by simple reduction method with the different mole ratios of L-ascorbic/citrate solution and stabilized with CTAB. The prepared three AgNPs were characterized by UV, fluorescence, FTIR, dynamic light scattering measurements and Scanning Electron Microscopy. The plasmon bands of AgNPs- reddish-brown (RB), green (G) and reddish-green (RG) were centered at 565, 587 and 592 nm, respectively. The highly luminescence emission was observed for AgNPs(G). The size diameters of the prepared AgNPs-G, RG and (RB) were measured by dynamic light scattering (DLS) method at 24.3 nm, 66.28 nm and 103.46 nm, respectively. The electrochemical properties of AgNPs-RG was recorded the oxidative part of AgNPs into Ag+ at +0.23 V and the reduction part of Ag+ into Ag0 was recorded at -0.49 V vs. Ag/AgCl). Cetyl trimethylammonium bromide (CTAB) was stabilized AgNPs(RG) which recorded in infrared and scanning electron microscope measurements. The concentration of thiourea, sodium sulphide was detected by the electrochemical sensitivity of AgNPs(RG)-CTAB. A calibration curve between electrochemical sensitivity of AgNPs-CTAB vs concentration of sulphur molecule. The limit of detection (LOD) was founded 2.10 and 1.90 µmole L-1 of sodium sulphide and thiourea, respectively (R2=0.94, n=3). The computational calculations are used to illustrated the chemical affinity of sulphur atom in sodium sulphide or thiourea towards AgNPs(RG).