Principles of refraction and extinction of electromagnetic radiation incident upon homogeneous isotropic condensed phases are reviewed. The relation between the complex refractive index,
n
(
ν
), and the attenuation constant,
k
(
ν
), through the Kramers–Kronig transform is shown as is the relation of these optical constants to
ɛ
, the complex dielectric function. The basis of the determination of the optical constants
n
and
k
as a function of frequency for transparent amorphous polymeric materials by reflection absorption infrared spectroscopy (RAIRS) is illustrated with examples. Also discussed is the effect of absorber concentration on the RAIR spectra. Various methods for the measurement of the optical constants and dielectric function of isotropic polymers included are other reflectance methods, attenuated total reflectance (ATR), transmittance–reflectance, transmission, and ellipsometry. The incipient importance of approaches for determining anisotropic optical constants is noted.