The moment when the speaker meets the Raven occurs towards the middle of the poem, specifically in the following two stanzas:
Open here I flung the shutter, when, with many a flirt and flutter,
In there stepped a stately raven of the saintly days of yore;
Not the least obeisance made he; not a minute stopped or stayed he;
But, with mien of lord or lady, perched above my chamber door -
Perched upon a bust of Pallas just above my chamber door -
Perched, and sat, and nothing more.
Then this ebony bird beguiling my sad fancy into smiling,
By the grave and stern decorum of the countenance it wore.
"Though thy crest be shorn and shaven, thou," I said, "art sure no craven,
Ghastly grim and ancient raven wandering from the Nightly shore -
Tell me what thy lordly name is on the Night's Plutonian shore!"
Quoth the Raven, "Nevermore."
Basically, the words "beguiling my sad fancy into smiling by the grave and stern decorum of the countenance it wore" mean that the speaker feels curious at the "attitude" of the raven, and it makes him laugh (or smirk, smile) how the raven looks so serious, dignified, and regal considering that he is "just a bird".
Therefore, the emotions that the speaker first feels when he greets the raven are curiosity, mixed with a bit of empathy, if not sympathy, for this animal who chose to enter his home only to look down on him as if he were a bringer of something supernatural.
The narrator of Edgar Allan Poe's "The Raven" is "nearly napping" late in the evening when he first hears the tapping sound. He thinks little of it at first, assuming that it is only a late night visitor coming to see him. He becomes more curious, and then "wondering, fearing,/Doubting, dreaming." When he first sees the bird, it makes him smile, and he is happy to have this strange visitor to ease his sadness and boredom. He jokingly addresses the raven, and asks him why he has come to perch in his home. The narrator is, of course, surprised when the raven actually answers his question. He marvels at the bird's response, though it makes no sense to him at first.