In this paper, a method of measuring roll angle with hollow cube corner reflector (HCCR) is proposed. Firstly, the space coordinate vector relationship between the mirror and the autocollimator is established by using the Euler rotation relationship, and the structure of the HCCR is designed. Secondly, through the actual measurement of the HCCR reflector's angle sensitivity, the specific formula of roll angle measurement is obtained. The experimental results show that the method can be used to measure the roll angle, and the maximum root mean square (RMS) error is 15" in the range of 350", and the repeatability of the experiment is better than 2.7". On the basis of retaining the traditional autocollimator, the plane mirror is replaced with HCCR, which realizes the measurement of the roll angle of the autocollimator. This method does not change the internal structure of the autocollimator system, and there is no process error caused by special processing technology, so as to retain the autocollimator's own long measurement distance, high measurement accuracy, high system stability, and large range of measurement performance, and it can also be used in industrial production.