Ambient backscatter communication (AmBC) enables radio-frequency (RF) powered backscatter devices (BDs) (e.g., sensors, tags) to modulate their information bits over ambient RF carriers in an over-the-air manner. This technology also called "modulation in the air", thus has emerged as a promising solution to achieve green communications for future Internet-of-Things. This paper studies an AmBC system by leveraging the ambient orthogonal frequency division multiplexing (OFDM) modulated signals in the air. We first model such AmBC system from a spread-spectrum communication perspective, upon which a novel joint design for BD waveform and receiver detector is proposed. The BD symbol period is designed to be in general an integer multiplication of the OFDM symbol period, and the waveform for BD bit `0' maintains the same state within a BD symbol period, while the waveform for BD bit `1' has a state transition in the middle of each OFDM symbol period within a BD symbol period. In the receiver detector design, we construct the test statistic that cancels out the direct-link interference by exploiting the repeating structure of the ambient OFDM signals due to the use of cyclic prefix. For the system with a single-antenna receiver, the maximum-likelihood detector is proposed to recover the BD bits, for which the optimal threshold is obtained in closed-form expression. For the system with a multi-antenna receiver, we propose a new test statistic, and derive the optimal detector. Moreover, practical timing synchronization algorithms are proposed, and we also analyze the effect of various system parameters on the system performance. Finally, extensive numerical results are provided to verify that the proposed transceiver design can improve the system bit-error-rate (BER) performance and the operating range significantly, and achieve much higher data rate, as compared to the conventional design.