Environmentally friendly biopolymer-based wood adhesives are an inevitable trend of wood product development to replace the use of harmful formaldehyde-based adhesives. In this research, a new eco-friendly modified cassava starch waste-based adhesive via carboxymethylation (CMS), and blending with polyvinyl alcohol (PVA), tannic acid (TA) and green synthesized silver nanoparticles (AgNPs) was prepared. The effects of TA content on green synthesis of AgNPs (Ag-TA) and bio-adhesive nanocomposite properties were investigated. The use of 5 wt% TA for AgNPs synthesis (Ag-TA-5) resulted in a uniform particle size distribution. The plywood prepared with Ag-TA-5 provided the highest dry and wet shear strength at 1.95 ± 0.11 MPa and 1.38 ± 0.3 MPa, respectively. The water absorption and thickness swelling of this plywood remarkably decreased up to 10.99% and 6.79%, respectively. More importantly, the presence of Ag-TA in CMS/PVA adhesive successfully inhibited the invasion of mold and bacteria. Based on the cyclic delamination test, the adhesive bond durability of bio-adhesive containing Ag-TA-5 could meet the requirement of the AITC Test T110-2007 and was comparable to commercial adhesives. The added advantage of the prepared bio-adhesive was its synthesis from agro-waste products and possible economically viable production at industrial level.