Ruling out the other options.
Natural pollination would let a pea flower self-pollinate on its own, giving Mendel no control over which plants crossed, so this isn't his controlled technique.
Hybridisation just describes the overall goal of crossing two varieties, not the specific hands-on step of preparing a flower for a controlled cross.
Grafting is a method of asexually joining plant tissue and has nothing to do with pollination.
That leaves emasculation, removing a flower's anthers before they can self-pollinate, which is exactly the technique Mendel used to control his crosses. So the answer is option (D).