Explicit control of the crystalline phases and morphology of semiconducting BiVO4 crystals has been successfully synthesized via microwave-hydrothermal condition (MW-HT) without requiring any template/surfactant, doping of metal ions, and altering pH of reaction solution. Unambiguously, the crystalline phase of BiVO4 crystal has transformed from tetragonal zircon type (tz) to monoclinic scheelite (m) via mixed-phase (m-tz) by altering microwave-irradiation time at fixed microwave-irradiation power (800 W) without changing any precursor concentrations throughout the reaction. X-ray diffraction and Rietveld refinement studies confirmed the phase transformation of BiVO4 crystals that occurs by controlling the irradiation time (10-22 min) and temperature (116-195 degrees C). The changes in VO43- tetrahedron bond strength and bond length attributed to phase transitions in BiVO4 crystals were corroborated by Raman spectra. Field emission scanning electron microscope revealed the sequential growth and rational morphological evolution of spherical-shaped zircon type tz-BiVO4 particles to preferentially oriented (010) and (110)-faceted decahedron-shaped scheelite m-BiVO4 crystals. The UV-reflectance and photoluminescence analyses revealed reduction in the optical bandgap and efficient charge separation with tunneling of excitons through interfaces, owing to phase transitions from tetragonal to monoclinic in BiVO4 crystals. High-resolution transmission electron microscopy images revealed the formation of heterojunctions between both the phases of BiVO4 crystals. The photocatalytic degradation of Rhodamine-B dye under natural sunlight showed maximum efficiency of 95% with highest rate kinetics (kappa(avg) = 0.0718/min) using mixed-phase BiVO4 (m:tz-60:40) crystals, whereas under simulated sunlight, monoclinic phase BiVO4 crystals showed high degradation efficiency of 87% with low rate kinetics (kappa(avg) = 0.0436/min) for 200 min. The free-radical trapping tests revealed that superoxide radical (center dot O-2) and hydroxyl radical (center dot OH) are active radicals during photocatalysis. Significantly, the MW-HT synthesized mixed -phase BiVO4 retained photocatalytic activity and structural stability even after three cycles. These findings open possibilities for innovative design of highly efficient semiconductor photocatalyst for environmental remediation applications.