The standard addition method, also called known addition, often used in analytical chemistry, quantifies the analyte present in an unknown. This method is useful for analyzing complex samples where a matrix effect interferes with the analyte signal. In comparison to the calibration curve method, the standard addition method has the advantage of the matrices of the unknown and standards being nearly identical. This minimizes the potential bias arising from the matrix effect when determining the concentration.

Standard addition involves adding known amounts of analyte to an unknown sample, a process known as spiking. By increasing the number of spikes, the analyst can extrapolate for the analyte concentration in the unknown that has not been spiked. There are multiple approaches to the standard addition. The following section summarize each approach.

In classic polarography, the standard addition method involves creating two samples – one sample without any spikes, and another one with spikes. By comparing the current measured from two samples, the amount of analyte in the unknown is determined. This approach was the first reported use of standard addition, and was introduced by a German mining chemist, Hans Hohn, in 1937. In his polarography practical book, titled Chemische Analysen mit dem Polargraphen, Hohn referred this method as Eichzusatz, which translates to "calibration addition" in English. Later in the German literature, this method was called as Standardzugabe, meaning "standard addition" in English.

Modern polarography typically involves using three solutions: the standard solution, the unknown solution, and a mixture of the standard and unknown solution. By measuring any two of these solutions, the unknown concentration is calculated.

As polarographic standard addition involves using only one solution with the standard added – the two-level design, polarographers always refer to the method as singular, standard addition.

Outside the field of polarography, Harvey's book Spectrochemical Procedures was the next earliest reference book to mention standard addition. Harvey's approach, which involves the successive addition of standards, closely resembles the most commonly used method of standard addition today.

To apply this method, analysts prepare multiple solutions containing equal amounts of unknown and spike them with varying concentrations of the analyte. The amount of unknown and the total volume are the same across the standards and the only difference between the standards is the amount of analyte spiked. This leads to a linear relationship between the analyte signal and the amount of analyte added, allowing for the determination of the unknown's concentration by extrapolating the zero analyte signal. One disadvantage of this approach is that it requires sufficient amount of the unknown. When working with limiting amount of sample, an analyst might need to make a single addition, but it is generally considered a best practice to make at least two additions whenever possible.

Note that this is not limited to liquid samples. In atomic absorption spectroscopy, for example, standard additions are often used with solid as the sample.