Hydrocarbons play a key role in shaping the chemistry of the interstellar medium, but their enrichment and relation with carbonaceous grains and polycyclic aromatic hydrocarbons still lack clear observational constraints. Here we report on JWST NIRSpec + MIRI/MRS infrared observations (~3–28 μm) of the local ultra-luminous infrared galaxy (ULIRG) IRAS 07251−0248, which revealed the extragalactic detection of small gas-phase hydrocarbons, such as benzene (C6H6), triacetylene (C6H2), diacetylene (C4H2), acetylene (C2H2), methane (CH4) and methyl radical (CH3), as well as deep amorphous C–H absorptions in the solid phase. The unexpectedly high abundance of these molecules indicates an extremely rich hydrocarbon chemistry not explained by high-temperature gas-phase chemistry, ice desorption or oxygen depletion. Instead, the most plausible explanation is the erosion and fragmentation of carbonaceous grains and polycyclic aromatic hydrocarbons. This scenario is supported by the correlation between the abundance of one of their main fragmentation products, C2H2, and the cosmic-ray ionization rate for a sample of local ULIRGs. These hydrocarbons are outflowing at ~160 km s−1, which may represent a potential formation pathway for hydrogenated amorphous grains. Our results indicate that IRAS 07251−0248 might not be unique but represents an extreme example of the commonly rich hydrocarbon chemistry prevalent in deeply obscured galactic nuclei.