Older complex analysis textbooks state that $ \displaystyle \int_{-\infty}^{\infty}e^{-x^{2}} \ dx$ can't be evaluated using contour integration. But that's now known not to be true, which makes me wonder if you can ever definitely state that a real-valued integral can't be evaluated using contour integration.
Edit: (t.b.) a famous instance of the above claim is in Watson, Complex Integration and Cauchy's theorem (1914), page 79:

