The invention discloses a method for measuring residual solvent methanol in chloropyridine by a head-space gas chromatography. The method comprises the steps of matching an Agilent 7890A gas chromatograph with an FID detector and an Agilent 7694E head-space sampler; adopting an Agilent DB-624 chromatographic column, keeping the beginning column temperature being 40 DEG C for 3min, and then increasing the column temperature to 60 DEG C at the heating rate of 2 degrees centigrade/min, increasing the temperature to 115 DEG C at the heating rate of 9.2 degrees centigrade/min, and increasing the temperature to 240 DEG C at the heating rate of 30 degrees centigrade/min and keeping the temperature for 2min; and detecting that the column temperature is 250 DEG C and the sample inlet temperature is 150 DEG C. Within the range of 0.007503mg/ml-1.5006mg/ml, methanol is excellent in linearity (r=0.9998, n=6), the precision degree RSD is equal to 4.3%, and the recovery rate is 96.1%. According to the method for measuring residual solvent methanol in chloropyridine by the head-space gas chromatography, the operation is simple and quick, and the measured results are accurate and reliable, so that the medicine quality can be effectively controlled.