Not enough information. What kind of chart?
If the chart is an "XY (Scatter)" chart, then mathematically there is no
difference between the R-squared calculated by linear chart trendline, the
ATP Regression tool, LINEST (fitting a straight line) or the RSQ worksheet
function. Numerically, there may be a difference in Excel versions prior to
2003 because the algorithms used by ATP, LINEST, and RSQ did not use the
available numeric accuracy as efficiently as did the chart trendline.
If the chart is a "Line" chart, then both the R-squared and the trendline
estimated by the chart assume that predictor (x) values are 1,2,3,... even if
you specified different values.
Jerry