'As' has a p3 configuration while Se has a p4 configuration. Since p orbitals hold 6 electrons max between 3 of them (x, y, z), each p orbital holds 2. The most stable way to fill up p orbitals is to do px, py, pz, px, py, pz or in other words, fill up all 3 orbitals with 1 electron each and then go back and fill them up with the 2nd electron in each. Therefore, the p3 configuration of 1 electron in each of px, py, and pz is relatively stable.
Since Se has p4, it has 2 in px, and 1 in py and pz. Meanwhile, As has p3 so 1 in px, py, and pz. Ionization energy is basically telling you how hard it is to remove one electron from the ground state. It is EASIER to remove the electron in the px orbital of Se because you would be bringing it to a more stable state (ie 1 electron in each of px, py, and pz). It is HARDER to remove the electron in any orbital of As because you are already in a stable state.
Hence the ionization energy of As is higher than Se.