In this study, a layered olivine-type LiMnPO₄/functionalized-multiwall carbon nanotube (f-MWCNTs) composite is used as an electrochemically active material for the real-time detection of dopamine. A wet-chemical ultrasonication process is used to combine LiMnPO₄ with f-MWCNTs at room temperature. The composite was subjected to various structural, morphological and electrochemical studies. The blending of olivine-type LiMnPO₄ into the f-MWCNTs is revealed by TEM analysis. The electrochemical activities of the LiMnPO₄/f-MWCNTs composite are systematically investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) for the real-time detection of dopamine. Furthermore, the applicability of the as prepared LiMnPO₄/f-MWCNTs composite was extended for the detection of human serum (E48) and rat brain-serum (C7) samples with satisfactory recoveries for the real-time applications. All these studies revealed that the layered olivine-type LiMnPO₄/f-MWCNTs composite is a potential candidate in the field of electrochemical sensing.