The quality must be checked to prevent the deterioration of water availability for human consumption. Rapid industrialization and urbanization result in the deterioration of the water quality making the water unfit for human consumption and domestic purposes. Periodic assessment of the analytical parameters is essential for the protection, preservation and utilization of water resources. The present study gives a detailed analysis of physico-chemical parameters in Puthery, Ozhuginasery, Kothaigramam, Suchindram, Kakkamur south, Thamaraikulam north, Near the salt pan 2, Near the mangrove forest, Near the salt pan 1 and Sea mouth to assess the spatial distribution of surface water ions, water quality index (WQI) and sodium adsorption ratio (SAR) in Pazhayar river surface water from Kanniyakumari district, Tamil Nadu, India during 2016. The most of the station and all season in Pazhayar river surface water respect to sodium chloride type ions using geochemical evolution Piper trilinear diagram. Thus, the study concluded that the monsoon and post-monsoon seasons of Pazhayar river surface water are suitable for irrigation purposes in stations 1 to 6, but unsuitable for drinking purposes in all stations and seasons for human use.