Psion were a clever bunch, but like many companies in the early 90s they didn’t really do standards. Although the 3c and 3mx had a proper RS-232 serial port (albeit using a very odd connector), all of the earlier models used a proprietary protocol called the SIBO Serial Protocol. All Series 3 models used SSDs that also communicated using this proprietary protocol.
A significant part of developing this equipment involves working out how to emulate an SSD or Psion peripheral. Luckily, while trawling the Internet for Psion PDFs I found the Psion SIBO Hardware Development Kit. This book gives a breakdown of how to create equipment for the Psion Series 3 and 3a, including the controller chips needed, the Psion serial protocol, and how to write drivers for the Series 3 and 3a.