Thanks for the pic, but it does not help much when all the wires are black!All wires are black, but they are numbered 1-4.
The second terminal from the top is the main Neutral connection. If there are any black wires going into that from the programmer, they should be connected to the N terminal on the programmer. Check by the numbers; there may not be any.
The third terminal from the top has two grey wires, these should be going to the two motorized valves. If they are, the black wires should be connected to the L terminal in the programmer
There are two white wires! The top one is labelled "heating" and, I guess, goes to the motorized valve. I presume you mean the bottom one!The white cable coming in from the right is the cylinder stat.
This looks like a normal 2 core + earth. Check which terminals they go to in the box. One of them should have a black wire connected to the same terminal. This black wire should be connected to terminal 3 on the programmer
You should have one black wire over. This should be connected at the box to the brown wire from the heating valve. If it is, it connects to terminal 4 on the programmer.
I'm considering a room stat
What boiler (make and model) do you have?
Edit: Stupid question ! It's in the title