This study reports on the synthesis and characterization of an innovative CQDs–decorated porous g-C3N4 (CN) with PANI hybrid nanocomposite for the degradation of a host of toxic pollutants including ciprofloxacin in the environment. Display omitted •Novel CQDs–decorated PANI with porous CN synthesized via an in-situ polymerization.•CN-PANI-CQDs has excellent photocatalytic CIP degradation and stability performance.•Effectiveness of photocatalyst and the effect of interfering anions were outlined.•Degradation mechanism and pathways were investigated through LC–MS analysis.•The synthesized photocatalyst can be utilized for the removal of toxic pollutants. Metal-free photocatalysts are widely used to decontaminate aqueous solutions by eliminating toxic and non-biodegradable compounds. It is desirable to develop a photocatalyst with high charge separation and migration efficiency. The addition of carbon quantum dots (CQDs) to graphitic carbon nitride with polyaniline (PANI) can improve its light absorption abilities and reduce the recombination of holes and electrons. In this study, a novel CQDs decorated on PANI with hollow porous graphitic carbon nitride (CN) was fabricated via an in situ polymerization followed by an ultra-sonication. The optimal CQDs–loaded CN-PANI nanocomposite exhibited the high visible light absorption with a high specific surface area. Furthermore, better photocatalytic degradation of ciprofloxacin (CIP) was achieved under the visible light. The improved photocatalytic activity of CN-PANI-CQDs (5.0%) can be attributed to its higher charge separation, and destruction of recombination rate through the heterojunction of excited electrons among CN, PANI, and CQDs. This effect was further confirmed by high photocurrent intensity, low photoluminescence emission, and electrical resistance. In addition, different parameters including catalyst weight, initial CIP concentration, and interfering effect of anions during CIP removal were investigated. The main active species in the degradation of CIP were identified to h+, •OH, and •O2− through the scavenger test. The high reusability and stability of the photocatalyst composite were also verified. The degradation intermediates and reaction pathways were identified. Furthermore, the effectiveness of the photocatalyst was evaluated using different toxic pollutants including imidacloprid, tetracycline, phenol, and rhodamine B under similar conditions. The CQDs–decorated CN-PANI was proved as a promising material for efficient photodegradation of toxic pollutants in water.