Photosynthetic cell factories (PCF) utilize oxygenic photoautotrophic organisms, such as cyanobacteria, to harvest light energy to produce a variety of valuable chemicals and fuels, promoting a sustainable circular bioeconomy. However, challenges such as inefficient light utilization due to self-shading and excessive biomass growth divert resources from chemical production, limiting efficiency. This study aims to employ 3D printing and bioink to entrap engineered cyanobacteria within a transparent matrix of cellulose nanofibril hydrogel. This strategy restricts cell overgrowth, enables optimized light transmission, and mitigates self-shading while promoting targeted chemical production. Cellulose nanofibril hydrogels have been modified through high-degree TEMPO oxidation with methacrylated hemicellulose introduced as a photo-crosslinker. This approach enables the fabrication of complex 3D structures with increased dimension of geometry—enhancing scalability without expanding the surface area. A reliable bioink formulation has been developed to allow 3D-printed biofilms that enhance nutrient transport and cell viability. Preliminary results with the ink demonstrate the impact of tuning the hydrogel’s optical properties on its chemical production. Furthermore, by adjusting hemicellulose content from 0.5% to 2%, the rigidity of the printed structure increased tenfold, improving mechanical stability for large-scale applications. These biocompatible engineered living materials, used in conjunction with 3D printing technology, have the potential to be easily scalable and improve sustainability in the chemical industry. Future work will maximize chemical production efficiency by refining the optical properties of hydrogel scaffolds and functionalizing CO2 capture for improved carbon utilization.