Desilusionan comes from the verb desilusionar, meaning to disappoint or disillusion. It's a strong emotional word that goes beyond simple sadness.
In the song, the lyrics state, "La vida es un castillo de ilusiones / Que te desilusionan al derrumbarse" (Life is a castle of illusions / That disappoint you when they crumble). This word perfectly captures the heartbreak and shattered hopes the singer feels, making it a poignant and memorable choice.
The whole song is one man bargaining with an absence. He opens by announcing he has found her again, then admits in the very next breath exactly where: "Cada segundo en mis recuerdos" (every second, in my memories). She is everywhere except the room he is standing in. From there he stacks up the damage in plain, slightly dramatic terms. Life is "un castillo de ilusiones" (a castle of illusions) that lets you down the moment it falls, she "mataste mi mundo" (killed my world), and he is still there wanting her anyway.
What he actually asks for is small. "Vuelve, mi reina" (come back, my queen) is the line he keeps returning to, and the reasons he gives around it are the best writing in the song: "Que a mí la vida se me está acabando" (because my life is running out on me) and "Y aquí en mi pecho no caben más penas" (and here in my chest there is no room for more sorrow). Notice that the title line is a sentence he never finishes. "Si tú estuvieras" (if only you were here) is a conditional with nothing after it, sung five times and left hanging every time. That is the trick of the song. He cannot say what would be different, because it would be everything.