From the last two decades, white biotechnology, with particular reference to deploying enzyme bio-catalysis, has gained special research interest to valorize the bio-sources lignocellulosic biomass. In this context, ligninolytic enzymes from a white biotechnology background have tremendous potentialities to transform biomass following the green agenda. The enzyme-based white biotechnology is now considered a key endeavor of twenty-first century, as it offers socio-economic and environmental merits over traditional biotechnology, such as eco-friendlier processing conditions, no/limited use of harsh chemicals/reagents, high catalytic turnover, high yield, cost-effective ratio, low energy costs, green alternative of complex synthesis, renewability, reusability, and recyclability. Research efforts are underway, around the globe, to exploit naturally occurring biomass, as a green feedstock and low-cost substrates, to generate value-added bio-products, bio-fuels, and bio-energy. One core problem in developing an eco-friendlier and economical bioprocess is the pre-treatment of lignocellulosic biomass to entirely or partially remove the lignin barrier from cellulose fibers, thereby allowing the enzymes to access the cellulose fibers and generate the products of industrial interests. The entire process requires lignocelluloses deconstruction where ligninolytic enzymes in synergies with redox mediators systems have not explored much. The limited exploitation of ligninolytic enzymes with tremendous catalytic efficiencies has created a massive research gap that we have tried to cover herein. This review further insights the white biotechnology, also termed industrial biotechnology, which uses microorganisms and their unique enzyme system to facilitate the clean and sustainable deconstruction process. Graphic