The relaxation time and frequency spectra are vital for constitutive models and for insight into the viscoelastic properties of polymers, since, from the spectra, other material functions used to describe rheological properties of various polymers can be uniquely determined. In recent decades the non-integer order differential equations have attracted interest in the description of time-dependent processes concerning relaxation phenomena. The fractional Maxwell model (FMM) is probably the most known rheological model of non-integer order. However, the FMM spectrum has not yet been studied and used to describe rheological materials. Therefore, the goal of the present paper was to study the applicability of the relaxation spectrum of FMM to the description of the relaxation spectra of polymers. Based on the known integral representation of the Mittag-Leffler two-parameter function, analytical formulas describing relaxation time and frequency spectra of FMM model were derived. Monotonicity of the spectra was analyzed and asymptotic properties were established. Relaxation frequency spectrum grows for large frequencies with a positive power law, while the relaxation time spectrum decays for large times with a negative power of time. Necessary and sufficient conditions for the existence of the local extrema of the relaxation spectra were derived in the form of two trigonometric inequalities. A simple procedure for checking the existence or absence of the spectra extrema was developed. Direct analytical formulas for the local extrema, minima, and maxima are given in terms of model fractional and viscoelastic parameters. The fractional model parameters, non-integer orders of the stress, and strain derivatives of FMM uniquely determine the existence of the spectrum extrema. However, the viscoelastic parameters of the FMM, elastic modulus, and relaxation time affect the maxima and minima of the relaxation spectra and the values of their local peaks. The influence of model parameters on their local extrema was examined. Next, the applicability of the continuous–discrete spectrum of FMM to describe Baumgaertel, Schausberger and Winter (BSW) and unimodal Gauss-like relaxation spectra, commonly used to describe rheological properties of various polymers, was examined. Numerical experiments have shown that by respective choice of the FMM parameters, in particular by respective choice of the orders of fractional derivatives of the stress and strain, a good fit for the relaxation modulus experiment data was obtained for polymers characterized both by BSW and Gauss-like relaxation spectra. As a result, a good approximation of the real spectra was reached. Thus, the viscoelastic relaxation spectrum of FMM, due to the availability of the two extra degrees of freedom (non-integer orders of the stress and strain derivatives), provides deep insights into the complex behavior of polymers and can be applied for a wide class of polymers with unimodal relaxation spectra.