Molecularly imprinted polymers (MIPs) have been potential and versatile candidates for analyte detection. The ability to create materials with well-controlled nanofibers is of intense interest for a variety of applications. In recent years, two fascinating materials MIPs and nanofibers have been combined to facilitate and achieve greater benefits through pre-synthesized MIP nanoparticle or microsphere encapsulation into nanofibers via electrospinning or direct reaction conditions. On the other hand, there are few excellent reports where MIP reaction constituents were dissolved into uniform and homogeneous electrospinning solutions to achieve MIP electrospun nanofibers. This article is the very first review reporting on the development of MIP nanofiber preparation and their applications for the determination of several valuable compounds in various areas.