The simulation of the gas flow field and electrostatic field in the photoionization detector by COMSOL was conducted based on principle investigation in the present study. Under the guidance of simulation results, structural optimization was carried out to significantly reduce the dead volume of the ionization chamber, and finally, the relationship between offset voltage and collection efficiency was obtained which led to a remarkable increase in the collection efficiency of charged ions in the photoionization detector. Then an ionization chamber with low interference and fast response was developed. Then experiment was performed with toluene as a VOCs gas under the condition of optimal gas flow rate of 50 ml, UV lamp ionization energy of 10.86 eV. The results showed that the ion collection efficiency reached 91% at a bias voltage of 150 V. Moreover, a preferred linearity of 99.99% was obtained, and a ppb level of LOD can be achieved. The determination results well-fitted the relationship between offset voltage and the response value obtained in the simulation.