This study demonstrates electrochemical top gating of graphene using a solid polymer electrolyte, enabling higher electron and hole doping than standard back gating. In-situ Raman spectroscopy monitors doping, revealing distinct responses of the G and 2D peaks. The G peak stiffens and sharpens for both electron and hole doping, while the 2D peak shifts with doping: it increases for hole doping and softens for high electron doping. The intensity ratio of G and 2D peaks strongly depends on doping, making it a sensitive parameter for monitoring charge levels. Graphene, with its high carrier mobility and near-ballistic transport, is a promising material for nanoelectronics. Electrochemical top gating is crucial for polymer transistors and has been applied to nanotubes. Here, a top-gated graphene transistor achieves higher doping levels than previously reported, up to ~5×10¹³ cm⁻², due to a high gate capacitance from a nanometer-thick Debye layer. Raman spectroscopy is a powerful non-destructive technique for identifying graphene layers, structure, and doping. The G band at ~1584 cm⁻¹ and the 2D band at ~2700 cm⁻¹ are key features. Doping affects these peaks: the G peak stiffens and sharpens, while the 2D peak position changes with doping. The 2D/G intensity ratio is sensitive to doping, making Raman an ideal tool for monitoring Fermi level shifts. Theoretical simulations using Density Functional Perturbation theory (DFPT) confirm experimental results, showing that the 2D peak position is influenced by phonon frequencies and doping. The 2D peak's response to doping is distinct from the G peak, with significant softening for electron doping and hardening for hole doping. The 2D/G ratio is a strong function of gate voltage, enabling precise doping monitoring. The study highlights the potential of solid polymer electrolytes for electronic and molecular sensing, with high gate capacitance and minimal leakage current. The results demonstrate the effectiveness of Raman spectroscopy in monitoring doping levels, offering a sensitive and non-invasive method for characterizing graphene and its applications in nanoelectronics.This study demonstrates electrochemical top gating of graphene using a solid polymer electrolyte, enabling higher electron and hole doping than standard back gating. In-situ Raman spectroscopy monitors doping, revealing distinct responses of the G and 2D peaks. The G peak stiffens and sharpens for both electron and hole doping, while the 2D peak shifts with doping: it increases for hole doping and softens for high electron doping. The intensity ratio of G and 2D peaks strongly depends on doping, making it a sensitive parameter for monitoring charge levels. Graphene, with its high carrier mobility and near-ballistic transport, is a promising material for nanoelectronics. Electrochemical top gating is crucial for polymer transistors and has been applied to nanotubes. Here, a top-gated graphene transistor achieves higher doping levels than previously reported, up to ~5×10¹³ cm⁻², due to a high gate capacitance from a nanometer-thick Debye layer. Raman spectroscopy is a powerful non-destructive technique for identifying graphene layers, structure, and doping. The G band at ~1584 cm⁻¹ and the 2D band at ~2700 cm⁻¹ are key features. Doping affects these peaks: the G peak stiffens and sharpens, while the 2D peak position changes with doping. The 2D/G intensity ratio is sensitive to doping, making Raman an ideal tool for monitoring Fermi level shifts. Theoretical simulations using Density Functional Perturbation theory (DFPT) confirm experimental results, showing that the 2D peak position is influenced by phonon frequencies and doping. The 2D peak's response to doping is distinct from the G peak, with significant softening for electron doping and hardening for hole doping. The 2D/G ratio is a strong function of gate voltage, enabling precise doping monitoring. The study highlights the potential of solid polymer electrolytes for electronic and molecular sensing, with high gate capacitance and minimal leakage current. The results demonstrate the effectiveness of Raman spectroscopy in monitoring doping levels, offering a sensitive and non-invasive method for characterizing graphene and its applications in nanoelectronics.