The fabrication and application of a novel electrochemical detector (ED) with nano crystalline Ce-doped lead dioxide film chemically modified electrode (CME) for liquid chromatography (LC) were described. The Ce-doped PbO2 film was characterized by X-ray diffractometer (XRD) and scanning tunnel microscope (STM). The electrochemical behaviors of (R)-Salsolinol ((R)-Sal) at the CME were investigated by cyclic voltammetry ( CV) and differential pulse voltammetry (DPV). It was found that the CME exhibited an efficiently electrocatalytic effect on the current responses of (R)-Sal, ( R)-N-methylsalsolinol ((R)-NMSal) and monoamine neurotransmitters. In LC-ED, all (R)-Sal, ( R)-NMSal, dopamine (DA), norepinephrine ( NE), 3-methoxy-4-hydroxyphenylglycol ( MHPG), 3,4-dihydroxyphenylacetic acid ( DOPAC), 5-hydroxytryptamine (5-HT), 5-hydroxyindoleacetic acid (5-HIAA) and homovanillic acid (HVA) had good and stable current responses at the CME. The linear ranges of the nine analytes were over three orders of magnitude (R-2 > 0.995). The application of this method coupled with microdialysis sampling for the determination of (R)-Sal, ( R)-NMSal and monoamine neurotransmitters in Parkinsonian patients' cerebrospinal fluid (CSF) was satisfactory.