Benzene can be used as an HPLC solvent… in theory.
It is compatible with standard HPLC instrumentation and will not damage an HPLC column. However, we would not recommend using this solvent for two main reasons. First, it is strongly UV-absorbing so would not be suitable for UV-based detection methods. Second, it is a known carcinogen and therefore less safe than many other solvents which are available. If you need something with similar properties, we would suggest toluene. It is often used as a benzene substitute and is less toxic.