Allelopathy is an ecological process in which released chemicals modify the performance of neighbouring organisms, whereas phytotoxicity describes an inhibitory response to a substance under a defined assay and, by itself, does not demonstrate field-level allelopathy. This critical narrative review combines a structured re-screening of the literature with targeted updating through 21 August 2026. Searches used combinations of allelopath*, allelochemical*, phytotox*, bioherbicid*, hormesis, biostimulant*, rhizosphere, microbiome, formulation, resistance, and regulation; peer-reviewed studies were complemented by authoritative regulatory and resistance databases. Evidence was appraised according to experimental context and mechanistic strength, explicitly distinguishing field or whole-plant validation from controlled bioassays, experimentally supported molecular targets from physiological or omics associations, and computational predictions. The synthesis covers chemical diversity, botanical and microbial sources, agro-industrial by-products, mechanisms of phytotoxicity and low-dose responses, rhizosphere interactions, and formulation strategies. Important corrections emerge from this evidence hierarchy: strigolactones are carotenoid-derived apocarotenoid hormones/signals rather than sesquiterpenes; multi-target activity does not preclude resistance evolution; cyanobacterial responses cannot be directly extrapolated to weeds or crops; and hormetic stimulation under controlled conditions is not equivalent to reliable field biostimulant performance. The principal translational gaps are insufficient dose–response standardisation, limited crop-selectivity and field validation, variable biomass chemistry, incomplete carrier and non-target safety data, and regulatory uncertainty for multifunctional products. Allelochemicals therefore represent promising components of integrated crop protection, but their agronomic value depends on rigorous evidence, formulation-specific validation, and context-dependent deployment rather than on laboratory phytotoxicity alone.