The term Brahmin refers to the priestly class so it may not just be dependent on their birth as in the case of Ravan, but also the activities that they perform. According to the Brahmand Puran there are seven types of Rakshasas and the descendants of Agastya and Vishwamitra are referred to as Brahma-rakshas:
Aiḍaviḍa (i.e. Kubera), the descendent of Pulastya, who was Savyapiṅgala (? Tawny-coloured in the left side) became the king of all Yakṣas, all those Rākṣasas who were the descendants of Pulastya, and of all those cruel Brahmarākṣasas belonging to the families of Agastya and Viśvāmitra who still carried on the study of the Vedas and who performed regularly penances and holy rites.
The other three groups of Rākṣasas were the performers of Yajñas. They were Yātudhānas, Brahmadhānas and Vārtās. They were moving about during the day time and they were not nocturnal wanderers like other demons. Their four groups are remembered by the wise (learned men).
So it seems there were some Rakshas tribes that followed the Vedic injunctions and possibly they would be considered Brahmins amongst the Rakshas tribes.