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● Multiform (Y 0.95 Eu 0.05)PO 4 crystals were attained via hydrothermal reaction. ● Increasing MA content leads to a tetragonal (t-) to hexagonal (h-) phase transition. ● A higher pH or PO 4 3- content favors the crystallization of t-(Y 0.95 Eu 0.05)PO 4. ● The (Y 0.95 Eu 0.05)PO 4 phosphors showed structure/morphology-dependent luminescence. [Display omitted] With maleic acid (MA) as an original and efficient structure/morphology modifier, tetragonal (t-) and hexagonal (h-) structured (Y 0.95 Eu 0.05)PO 4 nano/microcrystals with the diverse morphologies of nanoparticles, nanospindles, nanosquares, nanodisks and microprisms have been successfully synthesized via hydrothermal reaction at 180 °C for 24 h. The systematic study demonstrated that solution pH, MA/(Y 0.95 Eu 0.05)3+ molar ratio and PO 4 3-/(Y 0.95 Eu 0.05)3+ molar ratio are three crucial factors that synergistically determine phase structure and crystal shape/size of the product, and the underlying mechanisms were proposed. Photoluminescence of the (Y 0.95 Eu 0.05)PO 4 crystals was revealed to be strongly morphology/structure dependent, which was discussed in detail in terms of excitation, emission, asymmetry factor of luminescence, quantum yield, fluorescence decay, emission color and thermal stability. [ABSTRACT FROM AUTHOR]