Sodium p-perfluorous nonenoxybenzenesulfonate (OBS), a novel alternative to perfluorooctane sulfonic acid (PFOS), has been widely used in various fields in China and has certain toxic effects similar to PFOS. This study monitored OBS and 15 legacy PFASs in surface water, sediment, soil, and crucian carp near a fluorochemical manufacturing factory (FMF) in Suqian, China, focusing on the emission, isomer-specific environmental fate, and transformation of OBS. One to four orders of magnitude higher concentrations of OBS than other polyfluoroalkyl substances (PFASs) in all samples indicate that industrial emission is an important point source of OBS in the surrounding environment. The concentrations of OBS in surface water, sediment, and soil decreased exponentially as the distance from the FMF increases. The proportions of OBS-c, the dominant isomer, increased in the order: water (75.5 ± 6.4%), sediment (85.7 ± 10%), fish (muscle: 94.1 ± 0.99%; blood: 93.5 ± 1.4%), suggesting its preferential accumulation in sediment and fish than other isomers. Mono-hydroxylated transformation products of OBS were first identified in water, sediment, and fish, suggesting its hydroxylation may exist in the real environment. The transformation of OBS may explain its significantly lower bioaccumulation than PFOS in fish. However, considering the higher BAF of OBS than the regulatory bioaccumulation criterion and the possible stronger toxicity of its transformation products, further studies on its bioaccumulation and transformation are warranted.