The present invention provides a cost-effective method of synthesizing phosphate salt of a metal such as Fe and Mn that can be used for electrode active material of a lithium secondary battery. A precipitation reaction is first carried out to produce a solid salt of the metal having a lower valence value, e.g. Fe(II) and Mn(II). The solid salt is then purified before it is oxidized to form the target phosphate salt of the metal having a higher valence value, e.g. Fe(III) and Mn(III). The invention exhibits numerous technical merits such as easier operation, higher purity, and less consumption of washing water, among others.