In light of the widespread use of fossil fuels and the resulting environmental pollution, it is crucial to develop efficient photocatalysts for renewable energy applications that utilize visible light. Organic photocatalysts based on β-ketoenamine offer several advantages, including facile preparation, high stability, structural controllability, and excellent photovoltaic properties. However, in previous studies, the synthesis of porous organic polymers (POPs) often involved long, high-temperature processes. In this study, POPs with donor (D)-acceptor (A) structure were constructed by utilizing various branched bridging groups and 2,4,6-triformylphloroglucinol, across multiple temperature gradients. Through adjustments in hydrothermal temperature, we successfully synthesized a series of POPs with varying enol-keto structure ratios. Among these POPs, the dimethoxybenzidine-POPs (DMDPOPs) with methoxy electron-rich branched chains exhibited superior photovoltaic performance, electron transfer rate, and photocatalytic activity compared to the dihydroxybenzidine-POPs (DHDPOPs) with electron-deficient hydroxyl branched chains. Notably, DMDPOP-30 demonstrated outstanding performance, achieving a conversion rate of 98% within 3 h. Additionally, other POPs exhibited favorable conversions (90%), further confirming the feasibility of this synthetic approach. Moreover, the synthesis of DMDPOP-30 was achieved under mild conditions at room temperature, highlighting its significant potential for practical applications.