The invention discloses an REVO measuring head B-axis zero error calibration method applied to a non-orthogonal coordinate measurement system and belongs to the field of precision test technologies and instruments. The method comprises the steps that a square ruler is placed on a flat plate which is placed horizontally, and one working face M of the square ruler is fixed after being adjusted to beparallel to the X-direction of a measuring machine; a flat ruler is fixed after being closely attached to a working face N perpendicular to the working face M of the square ruler; three principal axes of the measuring machine are kept static, an A-axis of an REVO measuring head is placed at an appropriate position, and a B-axis of the REVO measuring head rotates to detect two symmetric points onthe flat ruler; and according to calculation of B-axis angles of the two detection points, a zero error of the B-axis of the measuring head can be calibrated. According to the method, under the statethat the three principal axes of the measuring machine are static, the situation that the angle of a joint arm is changed due to measuring force generated in the calibration process, and consequentlyan additional calibration error is introduced is avoided, high-precision calibration of the zero error of the B-axis of the REVO measuring head is realized, and the method can be applied to precisionmeasurement.