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It is generally best to prune pear trees late in the summer. You will stimulate the least amount of re-growth by pruning after the trees have finished growing for the year and have hardened their wood. But they can be pruned anytime after they bloom.

Generally trees that bloom in early spring are pruned after they finish blooming--bradford pear fits into this category.
Bradford pears are a victim of their own vigorous growth. Every twig and limb seems convinced that it can head for the sky immediately after it sprouts. The result is many vertical branches crowded around the trunk, all reaching heavenward. Simple physics explains that the attachment of a vertical branch is weaker than one which extends at an angle more toward the horizontal. Though the upright oval form of this tree is attractive, the means by which it is achieved leads to weakness.

In addition, so many branches sprout from a trunk that they eventually crowd each other for available space. After ten to fifteen years, large branches on a Bradford pear begin to split and fall if the tree has been left unpruned. The best time to prune a Bradford pear is in the first few years of its life in your landscape. If you wait much longer, limbs will grow too large and their removal could ruin the shape of the tree. This is an excellent time to grab your pruning tools and help your Bradford pear live long and prosper.