Morphology‐Tailored Hydroxyapatite Nanocarrier for Rhizosphere‐Targeted Phosphorus Delivery

High hydrophilicity and soil fixation collectively hamper the delivery of phosphorus (P) released from conventional chemical phosphorus fertilizers (CPFs) to plant rhizosphere for efficient uptake. Here, a phosphorus nutrient nanocarrier (PNC) based on morphology‐tailored nanohydroxyapatite (HAP) is constructed. By virtue of kinetic control of building blocks with designed calcium phosphate intermediates, rod‐like and hexagonal prism‐like PNCs are synthesized, both having satisfactory hydrophobicity (water contact angle of 105.4–132.9°) and zeta potential (−17.43 to −58.4 mV at pH range from 3 to 13). Greenhouse experiments demonstrate that the P contents increase by up to 183% in maize rhizosphere and up to 16% in maize biomass when compared to the CPF. Due to the water potential gradient driven by photosynthesis and transpiration, both PNCs are stably transported to maize rhizosphere, and they are capable to counteract soil fixation prior to uptake by plant roots. Within the synergies of the HAP morphological characteristics and triggered phosphate starvation response, root anatomy confirms that two pathways are elucidated to enhance plant P replenishment from the PNCs. Together with structure tunability and facile synthesis, our results offer a new nanodelivery prototype to accommodate plant physiological traits by tailoring the morphology of HAP. With intentionally designed calcium phosphate intermediates, newly synthesized HAP‐based nanoparticles with two tailored morphologies are constructed to deliver P for plant uptake. Aided by plant water uptake, the hydroxyapatite (HAP) having satisfactory surface hydrophobicity and zeta potential can be stably transported through bulky soil to rhizosphere and then be absorbed by maize plant roots via two routes, for maintaining P homeostasis.