A combination of high-energy ball milling, vacuum filtering, and sedimentation processes has been demonstrated to be a useful approach to reduce, in a controlled way, the length of as-cast Fe73.5Si13.5Nb3Cu1B9 amorphous magnetic microwires (MWs) and annealed material at 550 °C in nitrogen conditions. Homogeneous compositional microstructures with fairly narrow size distributions between 1300 and 11.7 μm are achieved, exhibiting tunable response as a soft magnetic material and as a microwave absorber. From the magnetic perspective, the soft magnetic character is increased with smaller length of the MWs, whereas the remanence has the opposite behavior mainly due to the structural defects and the loss of the shape anisotropy. From the microwave absorption perspective, a novel potential applicability is tested in these refined microstructures. This innovation consists of coatings based on commercial paints with a filling percentage of 0.55% of MWs with different lengths deposited on metallic sheets. Large attenuation values around -40 dB are obtained in narrow spectral windows located in the GHz range, and their position can be varied by combining different optimized lengths of MW. As an example of this powerful mechanism for absorbing microwaves at specific frequencies, MW lengths of 2 mm and 50 μm are chosen, where precise tailoring of the minimum reflection loss (RL) is obtained in a range between 8.85 and 13.25 GHz. To confirm these experimental results, an effective medium standard model proposed for electrical permittivity is used. Experimental and theoretical results are consistent and these novel composites are also proposed as a feasible candidate for designing frequency-selective microwave absorbers on demand, with low filling percentages and high absorption intensity values.