Passenger Car Equivalent (PCE) is essential for transportation engineering to assess heavy vehicles’ (HV) impact on highway operations and capacity planning. Highway Capacity Manual 2010 (HCM 2010) used PCE values and percent of heavy vehicles to account the impacts on both highway planning and operation, however, PCE values in the latest version of HCM derived based on the steady and balanced two-lane-two-way (TLTW) traffic flows. The objective of the study is to identify PCE values for TLTW highway at various traffic volume with an emphasis on congestion conditions. This study introduces an analytical model, combining a headway-based and a delay-based algorithms, for estimating PCEs of HV on a TLTW highway. This study contributes to the literature by providing relationships among PCE, the traffic volume level (TVL) of both lanes, and the TVL duration on a TLTW highway. Traffic volume was categorized into five levels: TVL A (<250 pc/h), TVL B (250–375 pc/h), TVL C (375–600 pc/h), TVL D (600–850 pc/h), and TVL E (>850 pc/h). The results indicate that on a TLTW highway, the TVLs of both lanes and their durations have significant impact on PCE values. In general, PCE values increase as TVL duration increases. Trucks have much higher impacts on operation under unbalanced conditions of TVL A with D, TVL B with C, and TVL D with B, when duration time is greater than one hour. When both lanes are saturated, trucks’ effect on capacity diminishes over time, and PCE values are approaching to 1.0.