Phenol　is　important　for　the　manufacture　of　phenolic　chemicals.　The　current　cumene　process　for　phenol　production　requires　harsh　conditions　and　suffers　from　unwanted　side　products.　Nowadays,　the　one　step　conversion　of　benzene　to　phenol　has　received　much　attention.　However,　because　of　the　obscurity　in　benzene　C(sp2)–H　bond　activation　and　the　easy　oxidation　of　phenol,　the　direct　oxidation　of　benzene　to　phenol　is　challenging.　As　an　alternative,　the　photocatalytic　selective　oxidation　of　benzene　into　phenol　under　mild　conditions　is　considered　promising.　In　this　review,　we　systematically　summarize　the　recent　advance　of　heterogeneous　photocatalytic　oxidation　of　benzene,　including　those　of　design　principles　and　various　modification　strategies,　mechanistic　understanding　determined　based　on　in　situ　characterization　and　density　functional　theory　calculation,　factors　affecting　kinetics　of　the　reaction,　reactor　design　and　photocatalyst　deactivation.　It　is　envisaged　that　photocatalysts　made　up　of　single　atoms,　layered　double　hydroxides,　and　metal　clusters　are　good　candidates.　At　the　end　of　this　article,　the　perspective　of　catalyst　design　and　strategies　for　the　exploration　of　reaction　mechanism　are　discussed,　emphasizing　on　the　use　of　state-of-the-art　techniques.　Moreover,　the　design　of　photocatalytic　reactors　for　the　realization　of　the　photocatalytic　process　is　considered.　©　2023　Dalian　Institute　of　Chemical　Physics,　the　Chinese　Academy　of　Sciences