You should definitely take a note of all meter readings (electricity, gas, and water, if applicable) on the day you move in. Remember that some electricity meters have multiple readings for day & night usage, so be sure to read both dials (or push the button on newer digital meters to step through the various readouts).
If you think you are entitled to any council-tax discounts (low income, 25% single-person occupancy etc.), make sure you claim them as soon as you move in. Councils will allow backdating of these in certain circumstances, but they can be very awkward about it and refuse if they don't think you "showed good cause as to why you did not claim earlier."