The designed synthesis of an S-scheme heterojunction has possessed a great potential for improving photocatalytic wastewater treatment by demonstrating increased the photoredox capacity and improved the charge separation efficiency. Here, we introduce the fabrication of a heterojunction-based photocatalyst comprising bismuth oxychloride (BiOCl) and bismuth-based halide perovskite (BHP) nanosheets, derived from metal-organic frameworks (MOFs). Our composite photocatalyst is synthesized through a one-pot solvothermal strategy, where a halogenation process is applied to a bismuth-based metal-organic framework (CAU-17) as the precursor for bismuth sourcing. As a result, the rod-like structure of CAU-17 transforms into well-defined plate and nanosheet architectures after 4 and 8 h of solvothermal treatment, respectively. The modulation of the solvothermal reaction time facilitates the establishment of an S-scheme heterojunction, resulting in an increase in the photocatalytic degradation efficiency of rhodamine B (RhB) and sulfamethoxazole (SMX). The optimized BiOCl/BHP composite exhibits superior RhB and SMX degradation rates, achieving 99.8% degradation of RhB in 60 min and 75.1% degradation of SMX in 300 min. Also, the optimized BiOCl/BHP composite (CAU-17-st-8h sample) exhibited the highest rate constant (k = 3.48 × 10−3 min−1), nearly 6 times higher than that of the bare BHP in the photocatalytic degradation process of SMX. The enhanced photocatalytic efficiency can be endorsed to various factors: (i) the in-situ formation of two-components BiOCl/BHP photocatalyst, derived from CAU-17, effectively suppresses the aggregation of pristine BHP and BiOCl particles; (ii) the S-scheme heterostructure establishes a closely-knit interfacial connection, thereby facilitating efficient pathways for charge separation/transfer; and (iii) the BiOCl/BHP heterostructure enhances its capacity to absorb visible light. Our investigation establishes an effective strategy for constructing heterostructured photocatalysts, offering significant potential for application in photocatalytic wastewater treatment.