Several techniques are presented for characterizing the order of semiconducting polymers on different length scales, including: differential scanning calorimetry; solid-state nuclear magnetic resonance spectroscopy; transmission electron microscopy; and grazing incidence scattering. As the behavior of highly conjugated polymers can differ distinctly from the more classic, highly saturated polymers for which some of these techniques were originally developed (e.g. polyethylene), the hazards and pitfalls associated with applying these techniques to semiconducting polymers are also discussed.