Cancer is a long-standing disease, and the use of anticancer drugs can cause many different harmful side effects. Therefore, the quantitative analysis of anticancer drugs is crucial. Among all the analytical techniques that have been utilized for the detection of doxorubicin, electrochemical sensors have drawn exceptional consideration because they are simple, affordable, and highly sensitive. Manganese tetraphenylporphyrin decorated reduced graphene oxide (Mn-TPP/RGO), tetraphenylporphyrin decorated reduced graphene oxide (TPP/RGO), and reduced graphene oxide (RGO) nanostructure based glassy carbon electrodes (GCEs) were fabricated for the detection of doxorubicin (DOX). The synthesized materials were characterized by FTIR, scanning electron microscopy (SEM), ultraviolet-visible spectroscopy (UV/vis), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). Doxorubicin detection was performed using differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). Among the prepared electrodes, Mn-TPP/RGO modified GCE gave an optimum peak current at pH 3. The Mn-TPP/RGO modified electrode showed significant linear response range (0.1-0.6 mM); effective sensitivity (112.09 μA mM-1 cm-2); low detection limit (63.5 μM); and excellent stability, selectivity, repeatability, and reproducibility toward doxorubicin. With differential pulse voltammetry, LoD and sensitivity were 27 μM and 0.174 μA μM-1 cm-2, respectively. Real sample analysis was also performed in human serum, and it depicted reasonable recovery results for spiked doxorubicin.