The present disclosure provides a neural network-based method for calibration and localization of an indoor inspection robot. The method includes the following steps: presetting positions for N label signal sources capable of transmitting radio frequency (RF) signals; computing an actual path of the robot according to numbers of signal labels received at different moments; computing positional information moved by the robot at a tth moment, and computing a predicted path at the tth moment according to the positional information; establishing an odometry error model with the neural network and training the odometry error model; and inputting the predicted path at the tth moment to a well-trained odometry error model to obtain an optimized predicted path. The present disclosure maximizes the localization accuracy for the indoor robot by minimizing the error of the odometer with the odometry calibration method.