Initialization of a qubit in a pure state is a prerequisite for quantum computer operation. Qubits are commonly initialized by cooling to their ground states through passive thermalization or by using active reset protocols. To accurately quantify the initialization one requires a tool to measure the excited state population with sufficient accuracy given that the spurious excited state population may not exceed a fraction of a percent. In this Letter we propose a new technique of finding the excited state population of a qubit using correlations between two sequential measurements. We experimentally implement the proposed technique using a circuit QED platform and compare its performance with previously developed techniques. Unlike other techniques, our method does not require high-fidelity readout and does not involve the excited levels of the system outside of the qubit subspace. We experimentally demonstrated measurement of the spurious qubit population with accuracy of up to 0.01%. This accuracy enabled us to perform “temperature spectroscopy” of the qubit which helps to shed light on sources of the decoherence.