Application of herbicide for rice cropping is inevitable but notorious for its side effect of environmental pollution. Precision fanning will be one of important tools for the least input and sustainable fanning and could be achieved by implementation of the variable rating technology. If a device to detect weeds in rice field is available, herbicide could be applied only to the places where it is needed by the manner of the variable rating technology. The study was carried out to develop an algorithm of image processing to detect weeds in rice field using a machine vision system of multi-spectral digital images. A series of multi-spectral rice field picture of 560, 680 and 800 nm of center wavelengths were acquired from the 27th day to the 39th day after transplanting in the ineffective tillering stage of a rice growing period. A discrimination model to distinguish pixels of weeds from those of rice plant and weed image was developed. The model was proved as having accuracies of 83.6% and 58.9% for identifying the rice plant and the weed, respectively. The model was used in the algorithm to differentiate weed images from mingled images of rice plant and weed in a frame of rice field picture. The developed algorithm was tested with the acquired rice field pictures and resulted that 82.7%, 11.9% and 5.4% of weeds in the pictures were noted as the correctly detected, the undetected and the misclassified as rice, respectively, and 81.9% and 18.0% of rice plants in the pictures were marked as the correctly detected and the misclassified as weed, respectively.