Biwiring is based on a sound electrical idea. By running seperate wires to each speaker crossover section you reduce noise coupling between the two sections and this gives a cleaner sound.
The main idea is that energy stored in the crossover comes back out at some later time and this creates a noise current. Biwiring puts each crossover leg in parallel with a very low amplifer output impedance and the noise current is effectively shorted out. Without biwiring a part of the noise current flows through the other crossover leg and creates a voltage across its circuit elements. This smears the sound.
Or something like that, the details are lost in the mists of time. My EE training happened many decades ago and I don't remember the whole story.
You don't need theory though, it is simple enough to try and the results are audible. It works. Wire is cheap.