A new metal-free organic molecular as co-catalyst was developed, which could drastically enhance the photocatalytic performance of photocatalyst (eg. g-C3N4, MoS2 and TiO2). The enhancing photocatalytic activity was evaluated for photocatalytic degradation of organic dyes. It showed ultra-high photocatalytic rate (4.17 mg/gmin) and ultra-short time (about 6.0 min) for photocatalytic degradation of organic dyes (25 mg/ml). The enhanced photocatalytic performance was attributed to suppress recombination of photogenerated charges and provide a new photoredox reaction pathway under molecular co-catalyst assistance. The study represents a facile method to develop ultra-effectively photocatalyst for applications in production of green and renew-able energy carrier, H-2 from water, reduction of CO2, synthesis of fine chemicals and remediation of environmental pollutants.