In order to solve the calibration problem of the application of REVO 5-axis system,which was designed to be applied in the orthogonal coordinate measuring machines (CMMs) and non-orthogonal CMM,some techniques based on symmetrical and reversal principle for calibrating the parameters and error items of REVO probe head were proposed and discussed in detail. The calibration of the parameters and error items of REVO probe head in the non-orthogonal CMM was realized only by measuring some gauge blocks with one CMM axis moving in a short distance,which avoided the introduced error due to the motion errors of the CMM axes moving in a large scale. The accuracy and effectiveness of the calibration techniques was proved by experiments and practice. After the calibration and error compensation,the average measurement error was reduced to 0.8 μm from 18.1 μm. The results show that the proposed methods are easy to operate and be traced to the source,and with high accuracy.