Clean energy transition via utilizing biomass resources has been projected as an important climate change mitigation strategy. A vital characteristic of biomass is its localized nature; therefore, bioenergy utilization should follow decentralized planning. Agrarian countries like India can take benefit of its large agricultural biomass waste pool to produce clean renewable energy. However, prior knowledge of spatio-temporal distribution, competing uses, and biomass characteristics are necessary for successful bioenergy planning. This paper assesses biomass resource and its power generation potential at different agro-climatic zone levels in the state of Rajasthan, India considering crop residue biomass (25 different crop residues from 14 crops) and livestock manure (from cattle, buffalo, and poultry). Uncertainties associated with the availability of biomass and the power generation potential are assessed for each agro-climatic zone under different scenarios. Greenhouse gases (GHGs) emissions from biomass-based power generations are also estimated and compared with biomass-equivalent coal power plants. It is observed that the annual biomass power potential of Rajasthan is 3056 MW (2496 MW from crop residues and 560 MW from livestock manure). Scenario analysis suggests that the potential varies from 2445 to 6045 MW under different biomass availability and power plant operating conditions. Annual GHGs emissions due to biomass power generation is 5053 kt CO₂eq. Replacing coal-based power with biomass power would result in annual GHGs savings of 11412 kt CO₂eq. The paper also discusses various carriers and barriers viz. logistics, institutional, financial and technical in setting up decentralized bioenergy plants. Outcomes of the present study are expected to assist renewable energy planners in India.