The effect of the order-disorder transition on the band gap of kesterite Cu2ZnSnS4, an interesting material for solar cells, has been investigated by optical spectroscopy. The band gap energy (Eg) decreases continuously with increasing annealing temperature, Ta, and reaches its minimum at Ta ∼ 273 °C. Eg is about 200 meV higher in the most ordered state, than in the fully disordered state. Its value and the transition kinetic depend on the sample stoichiometry. A simplified model able to explain the order degree and stoichiometry effects on the Eg value is developed. Ordering results in narrower Raman peaks without affecting the shape of the photoluminescence spectrum—except for the change in Eg—or the characteristic energy of the exponential tail below the fundamental absorption edge. Although a prolonged annealing increases the order degree, the material properties are still influenced by residual disorder as well as by defects related to the off-stoichiometry composition.