During the last heatwave, I molished a couple of window-shaped panels of correx, covered with a layer of bubblewrap and a layer of foil (largely on the basis that these were the materials I had to hand), for ease of gaffer-taping over the west-facing upstairs window.
I'm not sure how effective it is at reflecting heat, on account of being the wrong side of some fairly efficient double-glazing, but it does an excellent job of blocking the sunlight[1] without impeding airflow the way the curtains do.
[1] Barakta is a troglodyte.