Here we describe a new and sensitive flow electrochemical detection system that employs a novel flow-field shaped solid electrode (FFSSE). The system was constructed with a 3D-printed thin-layer flow cell (TLFC) and a flat screen-printed FFSSE with USB connection. This interface facilitates continuous flow accumulation square-wave anodic stripping voltammetry (ASV). The flow distribution in the working space of TLFC was simulated using the finite element method (FEM) and the shape and configuration of electrodes were optimized accordingly. We demonstrated the electrochemical determination of Pb2+ using this newly designed TLFC-FFSSE detection system without removal of oxygen from samples. This TLFC-FFSSE based system showed an attractive stripping voltammetric performance compared to a traditional ASV based method. A linear range for detection of Pb2+ was found to be 0.5-100 μg/L (0.5 to 100 ppb) and a detection limit of 0.2 μg/L (0.2 ppb) was achieved in the presence of bismuth as codeposition metal. The system was further applied to detect Pb2+ in biological broths of methane fermentation. The electrochemical detection results were consistent with that obtained from atomic fluorescence spectroscopy (AFS) analysis and the average recovery was found to be 95.5-106.5% using a standard addition method. This new flow electrochemical detection system showed better sensitivity and reproducibility compared to a traditional ASV based method. Such a system offers great potential for on-site and real-time detection of heavy metals where compact, inexpensive, robust, and low-volume analysis is required.