This chapter discusses the rheology of linear and crosslinked polymers based on N‐vinylpyrrolidone and N‐vinylcaprolactam in different physical states, such as dilute solution, complex fluid, or molten fluid. A review of the basic concepts of rheology starting with the development of the Boltzman superposition principle is followed by an in‐depth discussion of linear viscoelasticity. The chapter introduces the concepts related to rheological models of viscoelasticity and how these relate to the dynamics of polymer systems. The basic definition of rheology is the science of flow and deformation of matter. Developments in computational rheology have improved the accuracy of both continuum mechanics and molecular dynamics‐based model predictions. Poly(vinyl pyrolidone) has also been evaluated as a rheology modifier and as an additive to generate porosity in electrospun nanofiber technology for tissue regeneration. Rheological characterization was conducted using a parallel plate rheometer at ambient conditions.