Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is one of the most promising hole transport layers that is widely used in high-performance optoelectronic devices. However, the hygroscopic nature and acidity of PEDOT:PSS is known to cause degradation in devices and decrease their performance. In this study, a new pyridine solid additive, 2,3-dihydropyridine (2,3-DHP) was incorporated into the PEDOT:PSS solution to improve its characteristics. A low-temperature solution-based spin-coating device was utilized to produce the thin films. From the results, the PEDOT:PSS@2,3-DHP (1 wt%) exhibited excellent optical characteristics. It also provided informative and controlled morphology when it was annealed at 100 oC, suggesting that PEDOT:PSS@2,3-DHP has a potential advantage in photovoltaic (PV) devices. Moreover, in the photodetection experiment utilizing LED of 380 nm, PEDOT:PSS@2,3-DHP showed a higher photocurrent response when compared with pristine PEDOT:PSS. It also significantly reduced sheet resistance and achieved superior electrical conductivity. Interaction between the 2,3-DHP, PEDOT, and PSS chains altered the mechanical properties of the PEDOT:PSS, leading to the modification in structural and electrical characteristics. Overall, these findings highlight the importance and applicability of PEDOT:PSS@2,3-DHP in a wide range of optoelectronic devices.