<p>In recent years, biomass-based sorbent materials have emerged as promising sustainable alternatives to conventional synthetic sorbents for hydrocarbon remediation. However, existing literature frequently treats petroleum contamination as a uniform substance, overlooking the distinct physicochemical demands of total petroleum hydrocarbon (TPH) fractions. To address this gap, this review provides a comprehensive, TPH-centric synthesis of recent advances in modified biomass sorbents, explicitly distinguishing itself from conventional oil spill reviews by treating TPH as a heterogeneous C₅–C₅₀ continuum. A systematic evaluation is conducted on the physicochemical properties of petroleum fractions, underlying sorption mechanisms, and the efficacy of physical, chemical, and advanced modification strategies. Quantitative comparative analyses reveal that while advanced hierarchical structuring (e.g., tubular-lamellar aerogels) can achieve exceptional sorption capacities exceeding 320 g/g and retain structural stability over 50 dynamic cycles, these performance gains often incur significant techno-economic penalties, such as biochar yield reductions of up to 40% during high-temperature activation. Furthermore, we critically benchmark kinetic behaviors and advocate for a shift from single-point, mass-based equilibrium capacities to a unified framework of multidimensional metrics, including mass-normalized capacity (mg/g²) and surface-area-normalized capacity (mg/m²). Finally, this review identifies critical commercialization barriers, including technology readiness level (TRL) stagnation and a lack of explicit life-cycle assessments (LCAs), and proposes an actionable roadmap integrating smart architectures, digital twin modeling, and standardized testing protocols to drive the rational, scalable deployment of next-generation TPH sorbents.</p>