A method for calibrating one or more compensation values utilized by a compensation device of a transmitter includes: obtaining a plurality of output signals which were sequentially generated by the transmitter by processing a pair of input signals according to multiple pairs of compensation values as a plurality of feedback signals, where each feedback signal corresponds to one of the multiple pairs of compensation values, determining a plurality of coefficients of a cost function according to the multiple pairs of compensation values and the feedback signals in an operation of calibration; and determining a pair of calibrated compensation values according to the coefficients and providing the pair of calibrated compensation values to the compensation device.