This study proposes a simple and effective method for determination of Al, Cd, Cu, Ni, and Zn in soil samples, associating ultrasound-assisted extraction and flame atomic absorption spectrometry (FAAS). Ultrasound-assisted extraction conditions were optimized using a central composite design. This method required small volumes of HCl, HNO3, and HF as an extraction solvent blend to ensure effective analyte extraction. Limits of detection and quantification were determined to assess the minimum accurate concentration of the studied elements that can be detected and quantified in a soil sample. Therefore, the ultrasound-assisted extraction was concluded as a simple and straightforward pretreatment technique to determine Al, Cd, Cu, Ni, and Zn concentrations in soil samples. Eight sites of agricultural and native forest areas of the city of Ponta Grossa and Guarapuava, State of Paraná, Brazil, were evaluated for metals, and compared with the reference values for trace elements provided by the Brazilian National Environment Council. Environmental assessment of soils from those eight sites was accomplished through Igeo, EF, CF, and PLI parameters, which aimed at the evaluation of agricultural sites in comparison with adjacent natural forest sites with no history of anthropogenic mobilization to determine the degree of the contribution of anthropogenic sources to metal concentrations. According to the Igeo, EF, and CF parameters, all sites were classified as unpolluted to moderately polluted and none or minor enrichment due to anthropogenic activities were noticed. PLI parameter evaluated the concentration of all studied metals in soils to stipulate an order of contamination, which was concluded as site 8 <site 4 <site 3 <site 7 <site 2 <site 6 <site 1 <site 5 for the sites under study.