Biofabrication, an advanced additive manufacturing process, employs computer-controlled 3D printing devices to construct objects layer by layer. Unlike traditional 3D printing, bioprinting utilizes cells and bioinks to create organ-like hydrogels, facilitating the proliferation of living cells. Despite its potential, the advancement of biofabrication is constrained by the limited availability of suitable bioinks. The emergence of biofabrication technologies highlights the critical need for biocompatible, printable, and multifunctional bioinks. To address this challenge, this dissertation investigates a novel material: polyvinyl alcohol bearing a styrylpyridinium group (PVA-SbQ). PVA-SbQ demonstrates exceptional capabilities for creating multifunctional hydrogels using various light-activated printing methods. Importantly, this process eliminates the need for toxic crosslinkers or photoinitiators, thereby enhancing cell viability and proliferation. This dissertation commences with an in-depth exploration of the design principles underlying PVA-SbQ hydrogels, elucidating their superior crosslinking performance and hydrogel properties. Subsequently, advanced techniques such as laser-direct writing, stereolithography (SLA) printing, and embedded printing are meticulously introduced as effective methods for biofabricating PVA-SbQ hydrogels. Furthermore, the synergistic combination of PVA-SbQ with other biomaterials such as cellulose is examined to enhance its properties. The findings demonstrate that high-resolution and biocompatible PVA-SbQ hydrogels can be printed rapidly by different methods. Beyond its potential in organ printing and cell behavior regulation, PVA-SbQ shows significant promise in biomedical applications such as organ patches, wearable devices, pattern encryption, and 4D printing. This dissertation provides a profound understanding of PVA-SbQ hydrogels in terms of rational design, biofabrication strategies, and their promising applications in biomedical engineering. We anticipate that this material, in conjunction with advanced printing techniques, will offer a robust strategy for biofabrication and propel advancements in the biomedical field.