Ferrites are promising photocatalysts as they absorb a considerable fraction of visible light. Herein, a novel in-situ simple tactic polycondensation method was used to produce n-type porous graphitic carbon nitride nanosheets over p-type CaFe2O4 particles resulting in a “quasi-polymeric” heterojunction. An interfacial electron trap state was created, as represented by an energy-resolved distribution of electron trap patterns in the g-C3N4/CaFe2O4, which traps excited electrons and prevents charge carrier recombination. When the CaFe2O4 precursor content in the g-C3N4/CaFe2O4composite was optimized, the degradation rates of ciprofloxacin and phenol are 2.3 and 2.1-fold higher in comparison to pristine g-C3N4, respectively. The g-C3N4/CaFe2O4 composite efficiently absorbed visible light and could separate and transport charge carriers through the p-n heterojunction. The efficient interfacial charge transport and separation achieved in the composite were validated using photoluminescence spectra and photoelectrochemical characterizations. Based on scavenger studies and electron spin resonance analysis, the most active radical species for the aforementioned pollutant degradation are holes and superoxide anion radicals. Mott-Schottky measurements and X-ray photoelectron spectroscopy confirmed the photocatalytic reaction mechanism is a Z-scheme charge carrier transport route based on the p-n heterojunction. Therefore, the g-C3N4/CaFe2O4 heterojunction offers a lot of promise for pollutant degradation that is both efficient and long-term.