In this study, a series of cage siloxanes (CS), e.g., three polyhedral oligomeric silsesquioxanes (SSQs) and one spherosilicate (SS) derivative, were applied as functional additives for the preparation of poly(lactic acid)-based (PLA) nanofibrillar membranes with an electrospinning technique utilizing an efficient spinning wire electrode setup. The impact of the additives' structure, chemistry, and electrospinning parameters on the obtained materials' morphology (scanning electron microscopy) and physicochemical (thermogravimetry, differential scanning calorimetry, contact angle analysis, air flow analysis) properties is discussed. It is presented that applying organosilicon additives may extend the already tuneable properties of the membranes produced by electrospinning performed under different conditions and that they enable to obtain nanofibres of smaller diameter, which in turn increases the membrane porosity. Furthermore, the solvent-assisted electrospinning method allowed for unparalleled mixing of the PLA matrix with the CS additives, as no traces of free additives were visible on the membranes by scanning electron microscopy (SEM) imaging. The resulting membranes can be utilized as filter materials.