With the development of science and the continuous progress of artificial intelligence technology, Large Language Models (LLMs) have begun to be widely utilized across various fields. However, in the field of psychological counseling, the ability of LLMs have not been systematically assessed. In this study, we assessed the psychological counseling ability of mainstream LLMs using 1096 psychological counseling skill questions which were selected from the Chinese National Counselor Level 3 Examination, including Knowledge-based, Analytical-based, and Application-based question types. The analysis showed that the correctness rates of the LLMs for Chinese questions, in descending order, were GLM-3 (46.5%), GPT-4 (46.1%), Gemini (45.0%), ERNIE-3.5 (45.7%) and GPT-3.5 (32.9%). The correctness rates of the LLMs for English questions, in descending order, were ERNIE-3.5 (43.9%), GPT-4 (40.6%), Gemini (36.6%), GLM-3 (29.9%) and GPT-3.5 (29.5%). A chi-square test indicated significant differences in the LLMs' performance on Chinese and English questions. Furthermore, we subsequently utilized the Counselor's Guidebook (Level 3) as a reference for ERNIE-3.5, resulting in a new correctness rate of 59.6%, a 13.8% improvement over its initial rate of 45.8%. In conclusion, the study assessed the psychological counseling ability of LLMs for the first time, which may provide insights for future enhancement and improvement of psychological counseling ability of LLMs.