Industrial and urban settings emit substantial waste heat, accelerating greenhouse gases, ozone depletion, and thermal pollution. This research introduces an IoT-enabled automation framework powered by PVDF pyroelectric nanofiber sensors to address lack of sustainable, tamper-proof emissions control. These sensors detect, quantify, and harvest thermal emissions from HVAC, industrial machinery, and other heat-intensive sources. Unlike conventional systems, ours integrates real-time monitoring with dual-purpose energy harvesting, repurposing surplus energy to power environmental IoT devices. Emissions data activates automated mitigation—adaptive cooling, smart ventilation, and air purification—via a responsive networked layer. A blockchain-secured emissions ledger ensures immutable recordkeeping, regulatory compliance, and decentralized security. While pyroelectric harvesting is limited in low-emission zones, PV hybridization enhances sustainability. Results show ± 0.1 °C sensing accuracy, 3.6 V peak voltage in high-emission zones, strong responsiveness to dynamic emissions, and reliable autonomous mitigation. This is the first integrated solution combining piezoelectric/pyroelectric sensors, IoT automation, and decentralized blockchain security.