Raman spectroscopy has been widely used to measure thermophysical properties of 2D materials. The local intense photon heating induces strong thermal nonequilibrium between optical and acoustic phonons. Both first principle calculations and recent indirect Raman measurements prove this phenomenon. To date, no direct measurement of the thermal nonequilibrium between optical and acoustic phonons has been reported. Here, this physical phenomenon is directly characterized for the first time through a novel approach combining both electrothermal and optothermal techniques. While the optical phonon temperature is determined from Raman wavenumber, the acoustic phonon temperature is precisely determined using high-precision thermal conductivity and laser power absorption that are measured with negligible nonequilibrium among energy carriers. For graphene paper, the energy coupling factor between in-plane optical and overall acoustic phonons is found at (1.59-3.10) × 10 W m K, agreeing well with the quantum mechanical modeling result of 4.1 × 10 W m K. Under ≈1 µm diameter laser heating, the optical phonon temperature rise is over 80% higher than that of the acoustic phonons. This observation points out the importance of subtracting optical-acoustic phonon thermal nonequilibrium in Raman-based thermal characterization.