It is made from two prisms of a birefringent material such as calcite, usually cemented together.
In the second component prism the s-polarized ray remains ordinary (o-ray, polarized perpendicular to the optical axis), while the p-polarized ray becomes extraordinary (e-ray), with a polarization component along the optical axis.
As a consequence, the s-polarized ray is not deflected since the effective refractive index does not change across the interface.
The Sénarmont prism is similar in construction and action to the Rochon prism, as in both polarizers the ray that is not deflected is the o-ray after the internal interface, while the deflected ray is the e-ray.
However, in the Rochon prism, it is the p-polarized ray that remains an o-ray on both sides of the interface, and is therefore not deflected, while the s-polarized ray changes from o-ray to e-ray and is therefore deflected.