In addition to a marked rise in marine biodiversity, the Ordovician witnessed the most profound increase in the complexity of marine ecosystems in the history of the earth, including the expansion of tiering and enhanced biotic interactions. In order to understand these changes, it is important to study palaeoecological relationships among organisms at the commencement of the Great Ordovician Biodiversification Event (GOBE). Here, we describe sclerobionts associated with one of the earliest bryozoans in the fossil record, the oldest known trepostome, Orbiramus from the Fenhsiang Formation (late Tremadocian) of Hubei Province, China. These sclerobionts are diverse and include borings (e.g. Trypanites and Sanctum), bioclaustrations of vermiform organisms, and syn-vivo fouling by the putative black coral Sinopathes and other bryozoans. Diverse sclerobiotic associations and intricate palaeoecological relationships had already been established between bryozoans and other metazoans by the Tremadocian, showing the early onset of the 'hard substrate revolution' during the GOBE.