**Abstract**

In recent decades, plenty of nanomaterials have been investigated as electrocatalysts for the replacement of the expensive platinum (Pt) counter electrode in dyesensitized solar cells (DSSCs). The key function of the electrocatalyst is to reduce tri-iodide ions to iodide ions at the electrolyte/counter electrode interface. The performance of the electrocatalyst is usually determined by two key factors, i.e., the intrinsic heterogeneous rate constant and the effective electrocatalytic surface area of the electrocatalyst. The intrinsic heterogeneous rate constant of the electrocatalyst varies by different types of materials, which can be roughly divided into five groups: non-Pt metals, carbons, conducting polymers, transition metal compounds, and their composites. The effective electrocatalytic surface area is determined by the nanostructure of the electrocatalyst. In this chapter, the nanostructural design and engineering on different types of Pt-free electrocatalysts will be systematically introduced. Also, the relationship between various nanostructures of electrocatalysts and the pertinent physical/electrochemical properties will be discussed.

**Keywords:** counter electrode, dye-sensitized solar cells, electrocatalyst, nanostructure
