A simple, low cost and highly sensitive catalytic hydrogen signals (CHSs) technique has established for the investigation of Manganese(II) by means of ammonium 4-phenylpiperazine-1-dithiocarbamate and ammonium 4-benzylpiperidine-1-dithiocarbamate in various ecofriendly and biological matrices using D.C. polarography. This procedure was initiated on the reaction of Manganese(II) in APP-DTC/ABP-DTC in the existence of NH4Cl-NH4OH medium at pH 6.6 and 7.2 respectively. The resulting oxidation signals were obtained at -0.78 V and -0.64 V vs SCE, owing to the CHSs. Different experimental conditions such as pH effects, background electrolyte (NH4Cl-NH4OH) effects and DTCs and Manganese(II) ion effects have been studied. The current procedure was effectively applied for the testing of Manganese(II) in sundry environmental and biological samples and attained recovery percentages (95-99%) are comparable to the Atomic Absorption Spectrophotometry (AAS) method.