The shear behavior of polymers obtained by means of devices such as capillary and cone-and-plate rheometers is commonly used to assess their processing and as a characterization tool. However, the number of instances when two polymers have the same shear properties but perform differently during certain types of processing operations (e.g. film blowing and sheet extrusion) indicate that shear properties alone may not be sufficient to characterize polymeric fluids. We begin by defining the kinematics of shear free or extensional flow and the associated material functions. The extensional and shear behavior of three different types of polyethylene (PE) are then compared to illustrate the points that one cannot ascertain the extensional properties of polymer melts from their shear properties and, furthermore, there may not be a simple relation between properties obtained from one type of extensional flow and those of another type. The kinematics of most processing flows are extensional rather than shear in nature, and, hence, the performance of polymers during processes such as fiber spinning, film casting, film blowing, thermoforming, blow molding, and even extrusion is more readily accounted for through extensional viscosity measurements. Methods for carrying out extensional flow measurements are then reviewed including approximate methods. To illustrate the sensitivity of extensional viscosity measurements to subtle changes in the molecular architecture of PEs, results are presented for samples with a narrow molecular weight distribution but with varying numbers of long chain branches. Finally, constitutive equations which allow one to separate shear and extensional flow behavior are discussed as any attempts to simulate the subtle processing differences between two polymers will require constitutive equations of this nature.