The development of wide-spectrum responsive photocatalysts for efficient formaldehyde (HCHO) removal is highly desired yet remains a great challenge. Here we successfully converted zeolitic imidazolate framework-8 (ZIF-8), one of the most well-studied metal–organic frameworks (MOFs), from routine ultraviolet-driven to novel broad-spectrum-driven photocatalyst via a facile thermal treatment. The isocyanate groups (–NCO) formed in the thermally treated ZIF-8 (ZIF-8-T) is crucial in enabling the superior photocatalytic performance in formaldehyde degradation. Specifically, the best-performing ZIF-8-T sample showed around 2.1 and 9.4 times the HCHO adsorption amount and the solar photocatalytic degradation rate, respectively, of pristine ZIF-8. In addition, ZIF-8-T exhibited visible light (λ ≥ 400 nm) photocatalytic HCHO degradation performance, photo-converting 72% and nearly 100% of 20 ppm and 10 ppm HCHO within 1 hour, respectively. This work affords new insights and knowledge that inspire and inform the design and development of MOF-based photocatalysts with broad-spectrum responses for efficient air purification operations.