Third-order nonlinearity of monoclinic and orthorhombic phase of CuNb2O6 is studied in low power regime of 532 nm by Z-scan technique. In open aperture, monoclinic CuNb2O6 possess stronger saturable absorption due to the distorted structure arising from unequal arrangement of copper atoms. Closed aperture exposes the self-defocusing nature and orthorhombic phase exhibits stronger nonlinear refraction. Variation in third-order NLO coefficient due to change in phase and morphology of CuNb2O6 confirms the influence of sintering temperature and time. Microrod monoclinic CuNb2O6 possess maximum nonlinear absorption coefficient (6.47 × 10−3 cm/W) and pure orthorhombic CuNb2O6 attains maximum nonlinear refractive index (5.13 × 10−8 cm2/W) along with higher third-order nonlinear optical susceptibility (1.91 × 10−6 esu). Higher thermal nonlinearity resulted in stronger optical limiting action with pure orthorhombic CuNb2O6 (5.16 mW, 1.26 mW) compared to other phases. For understanding the material suitability for laser safety device, nonlinearity and limiting action of CuNb2O6 thin films were demonstrated. Earlier formation of monoclinic phase with morphology change (700 °C) and transition of monoclinic rich mixed orthorhombic phase to pure orthorhombic phase (900 °C) with increase in sintering time (3–12 h) was confirmed by XRD, FTIR and SEM analysis. Thus orthorhombic CuNb2O6 material with stronger self-defocusing and optical limiting action makes it more preference than monoclinic CuNb2O6 for third-order NLO applications. © 2018 Elsevier Ltd