These minerals differ in the ratio of magnesium to iron in the crystal structure; their composition ranges from pure magnesium silicate (MgSiO₃) to pure ferrous iron silicate (FeSiO₃). The series includes:

All except the theoretical end-member ferrosilite occur naturally. The magnesium-rich varieties commonly occur in ultramafic igneous rocks, the iron-rich varieties in metamorphosed iron-rich sediments. Orthopyroxenes are essential constituents of norite; they also are characteristic of charnockite and granulite. Aside from olivine, magnesium-rich (less than 30 percent iron) orthopyroxene is the commonest silicate in meteorites; it is a major constituent of most chondrites and an important component of mesosiderites and calcium-poor achondrites. For detailed physical properties, see pyroxene (table).

The orthopyroxene series crystallizes in the orthorhombic system (three crystallographic axes unequal in length and at right angles to each other). An analogue crystallizing in the monoclinic system (three crystallographic axes unequal in length with one oblique intersection), the clinoenstatite–clinoferrosilite series is found largely in meteorites (achondrites, chondrites, and mesosiderites).