Environmental remediation using sunlight is one of the most promising and cost-effective approaches to mitigate environmental hazards significantly related to the industrial development. In the present work, we report the synthesis of ZnO/ZnSe heterostructure via one-pot hydrothermal approach for the photocatalytic degradation of diazo dye i.e. Congo red. XRD analysis verified the crystal structure, phase purity and successful synthesis of the ZnO/ZnSe heterostructure photocatalysts. Moreover, the morphology and elemental composition of the photocatalysts were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron dispersive X-ray spectroscopy (EDX), respectively. The alignment of energy levels for the synthesized heterostructured photocatalysts was also drawn while using UV-visible diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). Finally, the as-synthesized heterostructures were employed as efficient photocatalysts for the degradation of Congo red under the illumination of UV-visible light. Our results indicated that ZnO/ZnSe heterostructure photocatalysts with maximum ZnSe content can efficiently degrade the dye up to 91% which might be attributed to the effective charge separation as extended solar absorption due to narrow bandgap of ZnSe.