Co-precipitation technique using copper (II) methylbutyldithiocarbamate prior to Nickel (II), manganese (II), cobalt (II), lead (II) and chromium (III) determinations their aqueous standard solutions by spectrophotometric method was developed in this study. The effect of pH, sample volume, amounts of methylbutyldithiocarbamate and copper (II) on the recovery of metal ions were studied. The heavy metals in the precipitate were determined by Flame Atomic Absorption Spectrophotometry (FAAS). The detection limits for the determination ranged from 0.003 mg/L to 0.006 mg/L. The coprecipitation procedure was applied for spectrophotometric determination of the heavy metals in water and sediment samples from River Ufara in Igbokoda of Ondo State, part of Nigeria where oil companies were at a time already operating. The mean concentration (ppm) of Ni, Mn, Co, Pb and Cr were 11.7 ± 5.5 and 13.2 ± 1.1; 18.7 ± 4.2 and 63.4 ± 18.2; 1.52 ± 0.11 and 5.60 ± 1.30; 7.8 ± 1.5 and 21.9 ± 3.2; 6.06 ± 0.80 and 19.5 ± 0.9 for water and sediment samples respectively. The mean concentrations of these metals for samples from this area were significantly different from corresponding concentrations for control samples which signified an evidence of metal pollution attributed to oil relating activities. There was also no significant difference in the concentrations of metals in samples using spectrometric technique with co-precipitation procedure and without co-precipitation procedure.