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The classroom - its layout, the teacher's desk for any lesson notes, where the resources are located (student's books, pencils, paper...); check through student's books if you are not sure as to the standard expected by the teacher in each subject...
If the teacher has left lesson plans - still bring you own lessons just in case.
The school's policy requirements (particularly about Behaviour Management and the expectations of Supply Teachers). Some schools have booklets for Supply Teachers which detail their expectations from dress code through to playground duty. Ask - they may have one.
Time to prepare any photocopying needed or to write the day and date onto the board and any information you would like the students to know i.e. Your name
Check the register for the names of the students and check the list of students who eat 'School Dinners' or who eat 'Packed Lunches' i.e. Lunches brought from home. Dinner ladies will come to the door and collect the students for each of these categories at lunch time.
If you have a Learning Assistant, introduce yourself and ask for information about classroom procedures and lesson information.
The students may have a special lining up place and you may need to collect them at the beginning of the day. Check it out.