Relationships between extinction and polarization parameters are explored using ultraviolet (ANS and IUE), visual, and infrared data along the same lines of sight. In particular, the well-known empirical relationship between polarization and extinction, p less than or equal to 9.0E(B - V), has been reexamined using lines of sight for which R(V), the ratio of total-to-selective extinction, is known. It is found that the amount of polarization per unit extinction p/A(V) is related to R(V) such that the maximum observed value of p/A(V) is smaller for large R(V). This implies that large grains are not efficient at producing polarization, which may be atributed to a reduced axial ratio or to less efficient alignment.