We propose novel triple- multipole orders as possible candidates for the two distinct low-temperature symmetry broken phases in quadrupolar system PrVAl. An analysis of the experiment under [111] magnetic fields indicates that the {\it ferro} octupole moments in the lower temperature phase arise from the {\it antiferro} octupole interactions. We demonstrate that the triple- multipole orders can solve this seemingly inconsistent issue. Anisotropies of quadrupole moments stabilize a triple- order, which further leads to the second transition to a coexisting phase with triple-${\bm q}$ octupole moments. The cubic invariant of quadrupole moments formed by the triple- components and the characteristic couplings with the octupole moments in their free energy play important roles. We analyze a multipolar exchange model by mean-field approximation and discuss the temperature and magnetic field phase diagrams. Many of the microscopic results, such as the number of phases and the magnitudes of critical fields in the phase diagrams, are qualitatively consistent with the experiments in PrVAl.

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