A simple, small and inexpensive photometer that uses a pair of light-emitting diodes (LEDs) and a simple operational amplifier was developed for investigating thiocyanate levels in saliva obtained from smokers and non-smokers. The photometer is based on paired emitter-detector diodes (PEDDs), and the entire system can be purchased for less than a hundred US dollars. The PEDD-based photometer can measure the transmittance of a solution in a 1-cm disposable polystyrene cuvette using only rechargeable dry-cell batteries, which makes it suitable for analysis outside of equipped laboratories. The metal complex formation between Fe (III) and thiocyanate ions in an acidic condition permits colorimetric detection of thiocyanate ions using LEDs emitting at 465 nm, because the complex shows maximum absorption at 457 nm. The developed photometer exhibits excellent performance with linearity ranging from 0.05 mmol L−1 to 0.75 mmol L−1 and a correlation coefficient (r2) > 0.999. The limits of detection and quantification were 0.01 mmol L−1 and 0.05 mmol L−1, respectively. Both intra- and inter-day precision were obtained with relative standard deviations (RSD) of less than 1% in the determination of thiocyanate. The proposed method is simple, facile, and sensitive enough to investigate the levels of thiocyanate in the saliva samples of smokers and non-smokers with centrifugation being the only special treatment for samples. The results showed that the concentrations of thiocyanate were approximately 5-fold higher in smokers than in non-smokers.