The third-order nonlinear optical properties of a series of resonance benzo[a]phenoxazinium salts in acetic acid solution were studied using the Z-scan technique employing a Nd:YAG nanosecond laser at 532 nm. The compounds displayed strong reverse absorption with third-order nonlinear optical coefficients of 0.42–1.20 × 10 −11 esu and second hyperpolarizabilities of 2.75–7.29 × 10 −29 esu, respectively. Quantum chemical calculations showed that the compound with more stable highest occupied molecular orbital energy also displayed highest second hyperpolarizability.