Motivated by the intersection theory of moduli spaces of curves, we introduce psi classes in matroid Chow rings and prove a number of properties that naturally generalize properties of psi classes in Chow rings of Losev-Manin spaces. We use these properties of matroid psi classes to give new proofs of (1) a Chow-theoretic interpretation for the coefficients of the reduced characteristic polynomials of matroids, (2) explicit formulas for the volume polynomials of matroids, and (3) Poincaré duality for matroid Chow rings.