Penta-graphene (PG) is a carbon allotrope that has recently attracted the attention of the materials science community due to its interesting properties for renewable energy applications. Although unstable in its pure form, it has been shown that functionalization may stabilize its structure. A question that arises is whether its outstanding electronic properties could also be further improved using such a procedure. As PG bilayers present both sp[Formula: see text] and sp[Formula: see text] carbon planes, it consists of a flexible candidate for functionalization tuning of electromagnetic properties. In this work, we perform density functional theory calculations to investigate how the electronic and structural properties of PG bilayers can be tuned as a result of substitutional doping. Specifically, we observed the emergence of different magnetic properties when boron and nitrogen were used as dopant species. On the other hand, in the case of doping with oxygen, the rupture of bonds in the sp[Formula: see text] planes has not induced a magnetic moment in the material.