This paper presents the segmentation technique used to segment the Worldview-2 high resolution satellite multispectral (MS) images. First the spectral features like Simple Ratio (SR), Normalized Difference Vegetation Index (NDVI), Soil Adjusted Vegetation Index (SAVI) and Modified Soil Adjusted Vegetation Index (MSAVI) are considered to extract the spectral features from the MS image. Next the MS image is segmented by using the over segmented k-means algorithm with novel initialization (OSKNI) method. The proposed method performs well in terms of User’s accuracy (UA), Producer’s accuracy (PA) and overall segmentation accuracy (OVA) compared to the existing k-means algorithm.