Microplastic contamination in terrestrial environments is an emerging concern, yet its association with agro-industrial activities and heavy metal contamination remains poorly understood. This study characterized microplastics in soils surrounding Labana Rice Mills, Birnin Kebbi, Nigeria, and assessed their co-occurrence with selected heavy metals. Soil samples were collected along four cardinal directions of the facility and analyzed using density separation, stereomicroscopy, and attenuated total reflection–Fourier transform infrared (ATR-FTIR) spectroscopy. Microplastic concentrations ranged from 626 ± 11 to 1112 ± 41 particles kg−1, with the northern axis having the highest. These concentrations were comparable to values reported for agro-environments in Bangladesh (660–1309 particles kg−1) and India (400–1370 particles kg−1). Pellets and fragments were the dominant shapes, while particle size 100–500 µm and transparent/white coloration predominated. Identified polymer types included polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride, and polyamide. Iron, copper, and zinc were detected in all samples and showed positive correlations with microplastic abundance (R2 = 0.72, 0.52, and 0.46, respectively; p < 0.01). Contamination factor indicated very high contamination across all axes, while pollution load index (PLI = 8.95) confirmed significant microplastic pollution. Polymer risk assessment classified polypropylene as low risk, polyethylene, polyethylene terephthalate, and polyvinyl chloride as moderate risk, and polyamide as high risk. The predominance of pellets suggests potential contributions from rice milling activities. The co-occurrence of microplastics and heavy metals highlights potential ecological risks and underscores the need for improved waste management practices, routine environmental monitoring, and targeted regulatory interventions in agro-industrial systems.