Electrowinning of metals from aqueous solutions has been used for over a century. It is the main recovery method for zinc, gold, silver, copper and cobalt. Lead alloys for anode are widely used because their desirable characteristics like low cost, reducing of power consumption and longer life time. So that the aim of the present work is to study the effect of addition of Ag and rapid solidification using melt spinning technique on the structure, physical and electrochemical properties of Pb-Sn-Ca alloys to be used as anode for electrowinning cell. Six rapidly solidified alloys of Pb-10Sn-2.5Ca-xAg (x = 0, 0.5, 1, 1.5, 2, 2.5 wt.%) were produced by melt-spinning technique. X-ray diffraction analysis and differential scanning calorimetry have been carried out. Also, mechanical, electrical and electrochemical properties were measured. Here we show that adding of Ag to Pb-10Sn-2.5Ca improves its mechanical properties. This is shown in the increase of Young's modulus and micro creep behavior as well as enhancement of corrosion resistance and electrical conductivity. Among the prepared rapidly solidified alloys, the Pb-10Sn-2.5Ca-1.5Ag in wt.% is considered as the one with the best composition to be used as anode for electrowinning cell.