This part of your fire risk assessment should be fairly obvious. In the event of a fire everyone is at risk. What you need to do as part of this process, though, is think about all the different people who might possibly be on your premises and also whether any of these may be at any increased risk due to who they are, where they work, the type of work they do, etc.
If you have a small premises where you just have a few full time staff and no-one else ever visits, your job here is pretty straightforward. However, most businesses are not that lucky. Consider people who only work for you infrequently or on a casual basis. Do you use contract workers? Do customers ever come onto your premises?
Anyone who might possible set foot on your premises must be considered, so that you can plan for their safety too. Do you have outlying parts of your premises where some people work either in isolation or small groups, such as outbuildings, stock yards, roof spaces, etc? Do not forget people who may be there when no-one else is, such as cleaners or overnight security staff.
If you have customers or members of the public on your site, you need to plan for the fact that they do not know your premises. How they react in an emergency will be different to staff who work there every day so you need to plan for how you deal with visitors. The same principle applies to any workers, such as contractors, who will also not know how to get around the building.
Give consideration to anyone who is less able to get around or be aware of an emergency. This might include disabled workers or visitors, people with visual or hearing impairment, young children or elderly people if you have customers on site.
If you use any staff for who English is not their first language, are they in danger of not understanding what is required of them in an emergency?