The fabrication of polyelectrolyte multilayer films (PEMs) using the Layer-by-Layer (LbL) method is one of the most versatile approaches for manufacturing functional surfaces. This is the result of the possibility to control the assembly process of the LbL films almost at will, by changing the nature of the assembled materials (building blocks), the assembly conditions (pH, ionic strength, temperature, etc.) or even by changing some other operational parameters which may impact in the structure and physico-chemical properties of the obtained multi-layered films. Therefore, the understanding of the impact of the above mentioned parameters on the assembly process of LbL materials plays a critical role in the potential use of the LbL method for the fabrication of new functional materials with technological interest. This review tries to provide a broad physico-chemical perspective to the study of the fabrication process of PEMs by the LbL method, which allows one to take advantage of the many possibilities offered for this approach on the fabrication of new functional nanomaterials.

使用逐层（LbL）方法制造聚电解质多层膜（PEM）是制造功能性表面的最通用方法之一。这是通过改变组装材料（构件）的性质，组装条件（pH值，离子强度，温度等）甚至可以通过随意控制LbL膜组装过程的结果。改变一些其他操作参数，这些参数可能会影响所得多层膜的结构和理化性质。因此，对上述参数对LbL材料组装过程的影响的理解在LbL方法潜在地用于制造具有技术兴趣的新功能材料的过程中起着至关重要的作用。