Vectorial structured light beams, characterized by their topological charge and non-uniform polarization distribution, are highly promising beam modes for several applications in different domains of optics and photonics. To harness its potential specifically in optical communication, data encryption, and optical trapping, it is necessary to tailor a multitude of these beams with arbitrary and large topological charge and polarization distribution. However, achieving the above-mentioned requires bulky optical setups that necessitate the superposition of two beams or involve complex material fabrication techniques that can directly generate these beams. In this paper, we report the generation of a large structured light beam array by utilizing multiplexed polarization holograms, computer-generated holography, and azo-carbazole polymer film. We have developed a theoretical framework for double-exposure polarization holography that enables the possibility of tailoring such a vectorial light beam array. Utilizing the developed theory, we showcase the experimental generation of a structured vector beam array of size 8 × 8 with arbitrary topological charges and polarization distribution in 3 mm × 3 mm area of the polymer film. Exploiting the large space bandwidth of the polymer film, we also demonstrate the generation of vector vortex beam arrays with exceptionally large topological charges (l=100). All the above has been experimentally realized by simply illuminating the hologram with a plane Gaussian beam, and no additional optics are needed. This reported method offers huge potential and opens up new possibilities for the utilization of vectorial structured light beams.